CN103814040B - Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst - Google Patents

Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst Download PDF

Info

Publication number
CN103814040B
CN103814040B CN201280045402.2A CN201280045402A CN103814040B CN 103814040 B CN103814040 B CN 103814040B CN 201280045402 A CN201280045402 A CN 201280045402A CN 103814040 B CN103814040 B CN 103814040B
Authority
CN
China
Prior art keywords
composition
group
formula
compositions
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201280045402.2A
Other languages
Chinese (zh)
Other versions
CN103814040A (en
Inventor
库尔特·布兰德施塔特
西蒙·库克
B·T·源
A·瑟格诺
R·泰勒
明-新·邹
阿斯维尼·达什
马修·奥尔森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of CN103814040A publication Critical patent/CN103814040A/en
Application granted granted Critical
Publication of CN103814040B publication Critical patent/CN103814040B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/66—Preparation of compounds containing amino groups bound to a carbon skeleton from or via metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—Compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07F—COIN-FREED OR LIKE APPARATUS
    • G07F13/00—Coin-freed apparatus for controlling dispensing or fluids, semiliquids or granular material from reservoirs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/74—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention discloses a kind of compositions, described compositions contains (A) catalyst for addition reaction of hydrogen and silicon and (B) aliphatic series unsaturated compound, and described aliphatic series unsaturated compound average per molecule has one or more unsaturated organic group of aliphatic series that can carry out hydrosilylation.Described compositions can be reacted by hydrosilylation and form product, such as silane, natural gum, gel, rubber or resin.Composition (A) contains metal ligand complex, and described metal ligand complex can be prepared by the method including making metal precursor and ligand reaction.

Description

Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst
Catalyst for catalyzing addition reaction of silicon with hydrogen is known in the art and commercially available.These routines Hydrosilylation catalyst can be the metal selected from platinum, rhodium, ruthenium, palladium, osmium and iridium.Or, hydrosilylation catalyst can be this Plant the compound of metal, such as chloroplatinic acid, six hydration chloroplatinic acid, platinous chloride, and described compound is organic with low-molecular-weight The complex of polysiloxanes or micropackaging platinum compounds in substrate or core/shell structure.Platinum and the organic poly-silicon of low-molecular-weight The complex of oxygen alkane includes 1,3-divinyl-1, the complex of 1,3,3-tetramethyl disiloxane and platinum.These complex can With micropackaging in resinous substrates.Exemplary hydrosilylation catalyst in United States Patent (USP) 3,159,601,3,220,972,3, 296,291,3,419,593,3,516,946,3,814,730,3,989,668,4,784,879,5,036,117 and 5,175, Described in 325 and EP0347895B.The hydrosilylation catalyst of micropackaging and the method preparing them are known in the art , such as United States Patent (USP) 4,766,176 and 5, illustrated in 017,654.
These hydrosilylation catalyst have the drawback that extremely expensive.Some metal in these hydrosilylation catalyst It is likely to be difficult to obtain, and some in these hydrosilylation catalyst is likely difficult to preparation.Need above-mentioned in the industry Conventional hydrosilylation catalyst replace with substitute that is less expensive and/or that be more easy to get.
Summary of the invention
Disclose the product of the composition comprising nickel precursor (Ni precursor) and part, and prepare described product Method.Described product and average per molecule tool can be comprised via the compositions of hydrosilylation formation product There is the aliphatic unsaturated compound of one or more unsaturated organic group of aliphatic series that can carry out hydrosilylation.When described When aliphatic series unsaturated compound lacks the hydrogen atom of silicon bonding, the most described compositions also comprises average per molecule and has one or many The SiH functional compound of the hydrogen atom of individual silicon bonding.
Detailed description of the invention
Except as otherwise noted, the most all quantity, ratio and percentage ratio are by weight.Unless the context of this specification Otherwise indicated, otherwise article " ", " a kind of " and " described " respectively refer to one (a kind of) or multiple (multiple).In the disclosure of scope Hold and include scope itself and any value included in it and end points.Such as, the disclosure of scope 2.0 to 4.0 is not only Including scope 2.0 to 4.0, but also individually comprise 2.1,2.3,3.4,3.5 and 4.0 and this scope included in any Other numerals.Additionally, the disclosure of the scope of such as 2.0 to 4.0 include subset such as 2.1 to 3.5,2.3 to 3.4,2.6 to 3.7 and 3.8 to 4.0 and this scope included in any other subset.Similarly, Ma Kushi group (Markush Group) disclosure include whole group and any separate member and included in subgroup.Such as, Ma Kushi group Group hydrogen atom, alkyl, the disclosure of aryl or aralkyl include single member's alkyl；Alkyl and aryl subgroup；And its Included in any other separate member and subgroup.
" alkyl " means the saturated univalence hydrocarbyl of acyclic, side chain or non-branched.The example of alkyl has but is not limited to methyl, second Base, propyl group (such as isopropyl and/or n-pro-pyl), butyl (such as isobutyl group, normal-butyl, the tert-butyl group and/or sec-butyl), amyl group (as Isopentyl, neopentyl and/or tertiary pentyl), hexyl, heptyl, octyl group, nonyl and decyl, and with 6 or more carbon atom The saturated univalence hydrocarbyl of side chain.
" aryl " means ring-type complete unsaturated alkyl.The example of aryl has but is not limited to cyclopentadienyl group, phenyl, anthracene Base and naphthyl.Monocyclic aryl can have 5 to 9 carbon atoms or 6 to 7 carbon atoms and or 5 to 6 carbon atoms.Multi-ring Aryl can have 10 to 17 carbon atoms or 10 to 14 carbon atoms and or 12 to 14 carbon atoms.
" aralkyl " means have pendant aryl and/or the alkyl of terminal aryl group or have the aryl of pendant alkyl group.Example Property aralkyl includes tolyl, xylyl, benzyl, phenethyl, phenyl propyl and phenyl butyl.
" carbocyclic ring " and " carbocyclic ring " each means hydrocarbon ring.Carbocyclic ring can be monocycle or can be multi-ring, the bridge condensed Connection multi-ring or screw togather multi-ring.Monocycle carbocyclic ring can have 3 to 9 carbon atoms or 4 to 7 carbon atoms and or 5 to 6 Carbon atom.Multi-ring carbocyclic ring can have 7 to 17 carbon atoms or 7 to 14 carbon atoms and or 9 to 10 carbon atoms.Carbocyclic ring Can be saturated or part is undersaturated.
" cycloalkyl " means saturated carbon ring.The example of monocyclic cycloalkyl is cyclobutyl, cyclopenta and cyclohexyl.
" halogenated hydrocarbon " means that the one or more hydrogen atoms being wherein bonded to carbon atom are taken by halogen atom the most in form The hydrocarbon in generation.Halogenation alkyl includes haloalkyl, halocarbon ring group and haloalkenyl group.Haloalkyl includes fluorinated alkyl, such as three Methyl fluoride (CF3), methyl fluoride, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoro propyls, 4,4,4-triRuorobutyl, 4,4,4,3,3- Five fluorine butyl, 5,5,5,4,4,3,3-seven fluorine amyl groups, 6,6,6,5,5,4,4,3,3-nine fluorine hexyls and 8,8,8,7,7-five fluorine are pungent Base；And chlorination alkyl such as chloromethyl and 3-chloropropyl.Halocarbon cyclic group include fluorinated cycloalkyl such as 2,2-difluorocyclopropyl, 2,3-difluoro cyclobutyl, 3,4-difiuorocyclohexyl and 3,4-bis-fluoro-5-methylcycloheptyl；With chlorination cycloalkyl such as 2,2-dichloro ring Propyl group, 2,3-dichloro cyclopenta.Haloalkenyl group includes allyl chloride.
" hetero atom " means http://www.iupac.org/fileadmin/user_upload/news/IUPAC_ Any one of the IUPAC periodic table of elements 13-17 race element of Periodic_Table-1Jun12.pdf, except carbon." miscellaneous former Son " include such as N, O, P, S, Br, Cl, F and I.
" containing heteroatom group " means to be made up of and also include at least one heteroatomic organic group carbon atom.Containing miscellaneous Atomic radical can include such as acyl group, amide, amine, carboxyl, cyano group, epoxy radicals, oxyl, imino group, ketone, ketoxime, sulfydryl, oxime And/or one or more in mercaptan.Such as, when containing one or more halogen atom containing heteroatom group, then containing miscellaneous former Subbase group can be halogenation alkyl as defined above.Or, when hetero atom is oxygen, then containing heteroatom group can be hydrocarbon oxygen Base such as alkoxyl or alkyl alkoxy.
" inorganic containing heteroatom group " means to be made up of at least 1 hetero atom and at least 1 hydrogen or different hetero atom Group.The one in such as amine, hydroxyl, imino group, nitro, oxo base, sulfonyl and/or mercaptan can be included containing heteroatom group Or many persons.
" miscellaneous alkyl " means also to comprise at least one heteroatomic acyclic, side chain or the saturated univalence hydrocarbyl of non-branched." miscellaneous Alkyl " include the alkyl that haloalkyl and at least one of which carbon atom have been replaced by the hetero atom of such as N, O, P or S etc, Such as when hetero atom is O, this miscellaneous alkyl can be alkoxyl.
" heterocycle " and " heterocycle " each means the cyclic group being made up of nuclear carbon atom and one or more hetero atom. Hetero atom in heterocycle can be N, O, P, S or combinations thereof.Heterocycle can be monocycle or can be condense multi-ring, Bridging multi-ring or screw togather multi-ring.Monocyclic heterocycles can have in ring 3 to 9 member atoms or 4 to 7 member atoms with And or 5 to 6 member atoms.Multi-ring heterocycle can have 7 to 17 member atoms or 7 to 14 member atoms and or 9 To 10 member atoms.Heterocycle can be saturated or part is undersaturated.
" heteroaromatic " means the group containing fully saturated ring being made up of nuclear carbon atom and one or more hetero atom. Monocyclic heteroaromatic groups can have 5 to 9 member atoms or 6 to 7 member atoms and or 5 to 6 member atoms. Polycyclic hetero-aromatic group can have 10 to 17 member atoms or 10 to 14 member atoms and or 12 to 14 members former Son.
Heteroaromatic includes heteroaryl such as pyridine radicals.Heteroaromatic includes heteroarylalkyl, i.e. has side chain heteroaryl and/or end The alkyl of heteroaryl or there is the heteroaryl of pendant alkyl group.Exemplary heteroarylalkyl includes picolyl and lutidines Base.
Abbreviation used herein is defined as follows.Abbreviation " cP " means centipoise, and " cSt " means centistoke." DP " means the degree of polymerization. " FTIR " means Fourier transform infrared spectroscopy." GC " means gas chromatography." GPC " means gel permeation chromatography.“Mn” Mean number-average molecular weight.Mn can use GPC to measure." Mw " means weight average molecular weight." NMR " means nuclear magnetic resonance, NMR.“Pa· S " mean pascal second, and " ppm " means PPM." COD " means cyclo-octadiene base." Et " means ethyl.“Me” Mean methyl." Ph " means phenyl." Pr " means propyl group and includes the various structures of such as iPr and nPr etc." iPr " means Isopropyl." nPr " means n-pro-pyl." Bu " means butyl and includes including the various structures of nBu, sec-butyl, tBu and iBu. " iBu " means isobutyl group." nBu " means normal-butyl." tBu " means the tert-butyl group." AcAc " means pentanedione complex. " 2-EHA " means 2-ethylhexanoate." OAc " means acetas." Hex " means hexenyl." THF " means oxolane. " Vi " means vinyl.
" M-unit " means have formula R3SiO1/2Siloxane unit, the most each R represents monovalent atoms independently or has Machine group." D-unit " means have formula R28iO2/2Siloxane unit, the most each R represents monovalent atoms or base independently Group." T-unit " means have formula RSiO3/2Siloxane unit, the most each R represents monovalent atoms or group independently.“Q- Unit " mean that there is SiO4/2Siloxane unit.
" nonfunctionalized " means that composition does not have the unsaturated substituent group of aliphatic series or the silicon bonding participating in hydrosilylation Hydrogen atom.
The amount " not containing " composition meaning that compositions contains cannot detect, or the amount of composition that compositions contains is not enough to The GC measurement result recorded as described in EXAMPLEPART is changed compared to the same combination saving this composition.Such as, originally Compositions described in literary composition can not catalyst made from platonic." not catalyst made from platonic " means that what compositions contained can be catalyzed and this combination In thing, the amount of the platinum catalyst of the hydrosilylation of the unsaturated group on other compositions cannot detect, or said composition contains The same combination that the amount of some platinum catalysts is not enough to compared to saving this platinum catalyst changes as described in EXAMPLEPART The GC measurement result recorded.Described compositions can be without conventional metallic catalyst.
What " metallic catalyst without conventional " meant that compositions contains can be catalyzed with on other compositions in said composition The metal selected from Pt, Rh, Ru, Pd, Os and Ir of hydrosilylation of unsaturated group or the compound of this metal Amount cannot detect, or the amount of conventional metallic catalyst that compositions contains is not enough to compared to saving this conventional metallic catalyst Same combination change the GC measurement result that records as described in EXAMPLEPART.Or, compositions as herein described is permissible Without catalyst for addition reaction of hydrogen and silicon (i.e. without being catalyzed composition hereinafter described in addition to composition as herein described (A) (B) any composition of the hydrosilylation of the aliphatic unsaturated group on).
There is at least one to be comprised by the compositions (compositions) of composition that hydrosilylation carries out reacting:
(A) catalyst for addition reaction of hydrogen and silicon Han Ni, and
(B) aliphatic series unsaturated compound, described aliphatic series unsaturated compound average per molecule have one or more can Carry out the unsaturated organic group of aliphatic series of hydrosilylation.
It is not bound by theory, it is believed that this contains Ni catalyst for addition reaction of hydrogen and silicon and may be characterized as can being effectively catalyzed this The hydrosilylation of compositions.The hydrosilylation of said composition can prepare product.This product can have Form selected from following: silane, natural gum, gel, rubber and resin.
When composition (B) does not contains the hydrogen atom of silicon bonding, then said composition also comprises composition (C) SiH functional compound, Described SiH functional compound average per molecule have one or more silicon bonding hydrogen atom, and be different from composition (A) and (B)。
Said composition can the most also comprise one or more other compositions, and one or more other compositions described are different In mentioned component (A), composition (B) and composition (C).The example of the most other composition has (D) spacer；(E) extender, increasing Mould agent or combinations thereof；(F) filler；(G) filler treatment agent；(H) Biocide；(I) stabilizer；(J) fire retardant；(K) table Face modifying agent；(L) cahin extension agent；(M) end-capping reagent；(N) flux；(O) age-inhibiting addition；(P) pigment；(Q) acid acceptor；(R) Rheologic additive；(S) vehicle；(T) surfactant；(U) corrosion inhibitor；And combinations thereof.
Composition (A) is containing Ni catalyst for addition reaction of hydrogen and silicon.This contain Ni catalyst for addition reaction of hydrogen and silicon comprise Ni precursor with The product of part or prepare by the product of Ni precursor with part.Be not bound by theory, it is believed that this instead Product is answered to comprise Ni-ligand complex.Ni precursor is different from Ni-ligand complex.Ni precursor is different from Ni precursor and part Product.
Ni precursor can be the metallic compound with formula (i): Ni-A2, the most each A independently be replaceable taking Dai Ji.Be not bound by theory, it is believed that one or more entities (instance) of A can be replaced from Ni by part and Form Ni-ligand complex.Be not bound by theory, it is believed that one or more entities of group A be by Ni precursor with Complex reaction between part is replaced and forms Ni-ligand complex.In formula (i), each entity of A can be identical or not With.The example of A includes halogen atom and monovalent organic groups.Monovalent organic groups can be that univalence hydrocarbyl or unit price are containing hetero atom Group.The unit price example containing heteroatom group has amino, halogenation alkyl, silazane base, carboxylic acid foundation (carboxylate Group), carboxylic acid ester groups, carbonyl, oxyl, sulfonate group, sulfimide base, acetic acid foundation (acetate group) and cyanogen Base.
In formula (i), the example of the halogen atom of A includes Br, Cl or I.Example for the monovalent halogenated alkyl of A Including haloalkyl, such as fluorinated alkyl such as CF3, methyl fluoride, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoro propyls, 4,4,4- TriRuorobutyl, 4,4,4,3,3-five fluorine butyl, 5,5,5,4,4,3,3-seven fluorine amyl groups, 6,6,6,5,5,4,4,3,3-nine fluorine hexyls With 8,8,8,7,7-five fluorine octyl group；And chlorination alkyl such as chloromethyl and 3-chloropropyl；Halocarbon ring group, such as fluorinated cycloalkyl such as 2,2-difluorocyclopropyl, 2,3-difluoro cyclobutyl, 3,4-difiuorocyclohexyl and 3,4-bis-fluoro-5-methylcycloheptyl；And chlorination Cycloalkyl, such as 2,2-dichloro cyclopropyl, 2,3-dichloro cyclopenta；And haloalkenyl group, such as allyl chloride.
In formula (i), the example of the univalence hydrocarbyl of A includes but not limited to alkyl, thiazolinyl, carbocylic radical, aryl and aralkyl Base.The example of alkyl has Me, Et, Pr, Bu, amyl group, hexyl, heptyl, ethylhexyl, octyl group, decyl, dodecyl, hendecane Base and octadecyl.The example of thiazolinyl has Vi, pi-allyl, acrylic and Hex.The example of carbocylic radical has saturated carbon ring group, such as Cycloalkyl such as cyclopenta and cyclohexyl；Or unsaturated carbon ring group, such as cycloalkenyl group such as cyclopentadienyl group, cyclohexenyl group or ring pungent two Thiazolinyl.The example of aryl has Ph, tolyl, xylyl, sym-trimethylbenzene. base and naphthyl.The example of aralkyl has benzyl and 2-benzene Ethyl.
In formula (i), the example of the amino of A has formula-NA "2, the most each A ' independently be hydrogen atom or unit price Alkyl.Exemplary monovalent alkyl for A ' includes but not limited to alkyl such as Me, Et, Pr, Bu, amyl group, hexyl, heptyl, ethyl Hexyl, octyl group, decyl, dodecyl, undecyl and octadecyl；Thiazolinyl, such as vinyl, pi-allyl, acrylic and Hex； Carbocylic radical, example has saturated carbon ring group (such as cycloalkyl, such as cyclopenta and cyclohexyl), or unsaturated carbon ring group is (such as ring penta 2 Thiazolinyl or cyclo-octadiene base)；Aryl, such as Ph, tolyl, xylyl, sym-trimethylbenzene. base and naphthyl；And aralkyl, such as benzyl Or 2-phenethyl.Or, each A ' can be hydrogen atom or the alkyl with 1 to 4 carbon atom, such as Me or Et.
Or, each A in formula (i) can be silazane group.
Or, each A in formula (i) can be carboxylate group.The example of the carboxylic acid ester groups being applicable to A includes but does not limits In OAc, ethylhexoate (such as 2-EHA), neodecanoic acid ester, caprylate and stearate.
In formula (i), the example of the monovalent hydrocarbon epoxide of A can have formula-O-A ", wherein A " is univalence hydrocarbyl.For A " the example of univalence hydrocarbyl include but not limited to alkyl, such as Me, Et, Pr, Bu, amyl group, hexyl, heptyl, ethylhexyl, pungent Base, decyl, dodecyl, undecyl and octadecyl；Thiazolinyl, such as Vi, pi-allyl, acrylic and Hex；Cycloalkyl, such as ring Amyl group and cyclohexyl；Aryl, such as Ph, tolyl, xylyl and naphthyl；Aralkyl, such as benzyl or 2-phenethyl.Or, often Individual A " can be alkyl, such as Me, Et, nPr, iPr, nBu, iBu or tBu.Or, each A " and can be alkyl, and or, often Individual A " can be Et, Pr (such as iPr or nPr) or Bu.
Or, each A in formula (i) can be alkyl, such as Me, Et, nPr, iPr, nBu, iBu or tBu.Or, often Individual A can be independently selected from Et, benzyl, sym-trimethylbenzene. base, Ph, NEt2、NMe2, cyclo-octadiene, ethylate, iPr, Bu, 2-EHA, Ethyoxyl, propoxyl group, methoxyl group and carbonyl.
Or, Ni precursor can be commercially available compound, as shown in table 1 below.
Table 1-Ni precursor
Ni precursor chemical title commercial source
Nickel dichloride. (II), dimethoxy-ethane adduct, minimum 97% Si Te Lyme company (Strem)
Ni-1 nickelous bromide (II), dimethoxy-ethane adduct, minimum 97% Si Te Lyme company
Double (1,5-cyclo-octadiene) nickel (0), 98+% Si Te Lyme company
Nickel diiodide. (II), anhydrous (99.5%-Ni) Si Te Lyme company
In Table 1, Si Te Lyme company (Strem) refers to think of spy's Lyme in Massachusetts, United States Newburyport city Xue Pin company (Strem Chemicals Inc., Newburyport, Massachusetts, U.S.A.).
Part is and the organic compound of Ni formation coordinate bond.In formula herein, monovalent organic groups can be single Valency alkyl or unit price are containing heteroatom group.The example of univalence hydrocarbyl includes but not limited to alkyl such as Me, Et, Pr, Bu, amyl group or own Base；Thiazolinyl such as vinyl, pi-allyl, acrylic and hexenyl；Carbocylic radical, example has saturated carbon ring group, and (such as cycloalkyl, such as ring Amyl group and cyclohexyl), or unsaturated carbon ring group (such as cyclopentadienyl group or cyclo-octadiene base)；Aryl, such as Ph and naphthyl；Aralkyl Base, such as benzyl, tolyl, xylyl, sym-trimethylbenzene. base or 2-phenethyl.
In formula, the unit price example containing heteroatom group includes halogenation alkyl or oxyl.The example bag of monovalent halogenated alkyl Include haloalkyl, such as fluorinated alkyl, such as CF3, methyl fluoride, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoro propyls and 4,4,4- TriRuorobutyl；And chlorination alkyl such as chloromethyl.The example of oxyl includes alkoxyl and aralkyl oxy.The example of alkoxyl There are OMe, OEt, OPr and OBu；Or OMe.The example of aralkyl oxy is Phenylmethoxy and phenyl ethoxy.Or, unit price Can be the aryl or aralkyl with one or more substituent group being bonded to nuclear carbon atom containing heteroatom group, wherein One or more in described substituent group contains hetero atom, the most above-mentioned aralkyl oxy or such as
WithEtc base Group, wherein * represents junction point.
Part can have a formula (ii):
In formula (ii), subscript x depends on Q1Quantivalence be 0 to 1 integer.Q1Selected from oxygen, sulfur, nitrogen and phosphorus.
In formula (ii), A1、A3、A4、A5And A6It is each independently selected from monovalent organic groups, hydrogen, halogen atom and nothing Machine contains heteroatom group, and precondition is A6It it not chlorobenzene.
In formula (ii), A2Selected from monovalent organic groups, hydrogen, halogen atom and inorganic containing heteroatom group.
Or, in formula (ii), A2With A3Can be bonded together and form ring structure.Or, A3With A4Can be bonded Form ring structure together.Or, A4With A5Can be bonded together and form ring structure.Or, A5With A6Can be bonded in Form ring structure together.This ring structure and the pyridine ring fusion in formula (ii).
The example of the part of formula (ii) include 483 in table 2,484,486,488,510,512,777,785,788, 799,805,819,2363,6269,8838,8842,8856,8945 and 8946.
Or, part can have a formula (iii):
In formula (iii), Q2It is oxygen or sulfur.
In formula (iii), A7、A8、A9、A10And A12Be each independently selected from monovalent organic groups, hydrogen, halogen atom and Inorganic containing heteroatom group.
In formula (iii), A11Selected from monovalent organic groups, hydrogen, halogen atom and inorganic containing heteroatom group, premise bar Part is A11It it not benzyl.
Or, in formula (iii), A7With A8Can combine and form ring structure.Or, A8With A9Can combine and shape Become ring structure.Or, A9With A10Can combine and form ring structure.Or, A11With A12Can combine and form ring structure.Logical The example of the part of formula (iii) includes 604 in table 2,2920,2921,6886,7282,7377 and 10364.
Or, part can have a formula (iv):
In formula (iv), subscript x depends on Q3Quantivalence be 0 to 1 integer.Q3Selected from oxygen, sulfur and nitrogen.
In formula (iv), A15、A16、A17、A18、A20And A21It is each independently selected from monovalent organic groups, hydrogen, halogen former Sub and inorganic containing heteroatom group.
In formula (iv), each A19Independently selected from monovalent organic groups, hydrogen, halogen atom and inorganic containing hetero atom base Group, precondition is that A19 does not contains diphenylphosphine.
Or, in formula (iv), A20With A21Can be bonded together and form ring structure.Or, A19With A18Can be with key It is combined and forms ring structure.Or, A18With A17Can be bonded together and form ring structure.Or, A17With A16Can be with key It is combined and forms ring structure.Or, A16With A15Can be bonded together and form ring structure.The part of formula (iv) Example include 755 in table 2,1430,1483,1832,2072,2915,2927,3472,3586,3746,3749,4098, 4117,5479,6870,7124,7471,7496,10132 and 10218.
Or, part can have a formula (v):
In formula (v), subscript x is the integer of 0 to 1, and this depends on Q4Quantivalence and Q4To A29It is with dotted line table The singly-bound shown or double bond.Subscript y is the integer of 0 to 1, and this depends on Q5Quantivalence and Q5To A31It is represented by dotted lines Singly-bound or double bond.
In formula (v), Q4And Q5It is each independently selected from N, O, P and S.
In formula (v), A25、A26、A27、A28、A29、A30、A31And A32Be each independently selected from monovalent organic groups, hydrogen, Halogen atom and inorganic containing heteroatom group.
Or, in formula (v), A29With A25Can be bonded together and form ring structure.Or, A25With A26Can be with key It is combined and forms ring structure.Or, A26With A27Can be bonded together and form ring structure.Or, A27With A28Can be with key It is combined and forms ring structure.Or, A28With A32Can be bonded together and form ring structure.
Or, in formula (v), A29With A30Can be bonded together and form ring structure, precondition is to be formed Ring structure is not pyrroles.Or, A31With A32Can be bonded together and form ring structure, precondition is formed ring knot Structure is not pyrroles.The example of the part of formula (v) include 165 in table 2,788,799,805,819,1116,1125,1214, 1547,3544,3547,4151,4202,7639 and 8749.
Or, part can have a formula (vi):
In formula (vi), subscript x depends on Q8Quantivalence be 0 to 1 integer.Q8Selected from N, O, P and S.
In formula (vi), A45、A46、A47、A49、A50、A51And A52It is each independently selected from monovalent organic groups, hydrogen, halogen Element atom and inorganic containing heteroatom group, precondition is to work as Q8Then A when being sulfur45It not benzene.
In formula (vi), A48Selected from monovalent organic groups, hydrogen and inorganic containing heteroatom group.
Or, in formula (vi), A45With A52Can combine and form ring structure.Or, A52With A51Can combine and shape Become ring structure.Or, A51With A50Can combine and form ring structure.Or, A50With A49Can combine and form ring structure.Or Person, A45With A46Can combine and form ring structure.The example of the part of formula (vi) includes 635,1249,1888,2061, 2062,2075,2272,3096,3191,4202,4990,5177,6253,6322,6340,6372,7124 and 7534.
Or, part can have a formula (vii):
In formula (vii), subscript x depends on Q10Quantivalence be 0 to 1 integer.Q10Selected from N, O, P and S.Dotted line Instruction singly-bound or double bond.
In formula (vii), A56And A57It is each independently selected from monovalent organic groups, hydrogen, halogen atom and inorganic containing miscellaneous Atomic radical.
In formula (vii), A58And A55It is each independently selected from monovalent organic groups, hydrogen or inorganic group.
Or, in formula (vii), A56With A57Can combine and form ring structure.Or, A55With A56Can combine and Form ring structure.The example of the part of formula (vii) include part in table 2 732,734,735,1936,2956,6417, 9042 and 10267.
Or, part can have a formula (viii):
In formula (viii), subscript x depends on Q11Quantivalence be 0 to 1 integer.SubscriptyDepend on Q12Chemical combination Valency is the integer of 0 to 1.Q11And Q12Being each independently selected from N, O, P and S, precondition is if Q11Or Q12It is that then they are not or not nitrogen It is imines nitrogen.Dotted line represents singly-bound or double bond.
In formula (viii), A60、A61、A65And A66Be each independently selected from monovalent organic groups, hydrogen, halogen atom and Inorganic containing heteroatom group.
In formula (viii), each A62, each A63And each A64Independently selected from monovalent organic groups, hydrogen, halogen Atom and inorganic containing heteroatom group.
Or, in formula (viii), A60With A61Can be bonded together and form ring structure.Or, A61With A62Permissible It is bonded together and forms ring structure.Or, A62With A63Can be bonded together and form ring structure.Or, A63With A64Permissible It is bonded together and forms ring structure.Or, A64With A65Can be bonded together and form ring structure.Or, A65With A66Permissible It is bonded together and forms ring structure.Or, A63With A61Can be bonded together and form ring structure.Formula (viii) joins The example of body include 748 in table 2,1214,1769,3499,3547,3746,3749,6322,6372,7534,8881, 8977,9042 and 9072.
Or, part can have a formula (ix):
In formula (ix), subscript x depends on Q17Quantivalence be 0 to 1 integer.Q17Selected from N, O, P and S.Q17Or Can be carbon, precondition be when Q17 is carbon, this carbon and A81Form carbonyl bond and and A80Form hydroxyl (such as part 2816)。Q18Selected from O and S.Q19Selected from hydroxyl and mercaptan.
In formula (ix), A82、A83、A84And A85It is each independently selected from monovalent organic groups, hydrogen, halogen atom and nothing Machine contains heteroatom group.
In formula (ix), A80And A81It is each independently selected from monovalent organic groups, hydrogen and inorganic containing heteroatom group.
Or, in formula (ix), A81With A82Can be bonded together and form ring structure.Or, A82With A83Can be with key It is combined and forms ring structure.Or, A83With A84Can be bonded together and form ring structure.Or, A84With A85Can be with key It is combined and forms ring structure.The example of the part of formula (ix) includes the part 2816,3500 and 3505 in table 2.
Or, part can have a formula (x):
In formula (x), subscript x depends on Q16Quantivalence be 0 to 1 integer.Q16Selected from N, O, P and S.Q14It is selected from Oxygen and sulfur.Q15Selected from hydroxyl and mercaptan.
In formula (x), each A76Independently selected from monovalent organic groups, hydrogen, halogen atom and inorganic containing hetero atom base Group.
In formula (x), A77And A78It is each independently selected from monovalent organic groups, hydrogen or inorganic group.
In formula (x), or, in formula (x), A76With A77Can be bonded together and form ring structure.Or, A77With A78Can be bonded together and form ring structure.The example of the part of formula (x) includes 2363,2806 and 4226.
Or, part can have formula (xi)
In formula (xi), subscript x depends on Q50Quantivalence be 0 to 2 integer.Q50Selected from N and C.Subscript y and z are each From be independently 0 to 1 integer, this depend on respectively with A90And A88The quantivalence of the N connected.Dotted line instruction singly-bound or double bond. The two nitrogen-atoms can be positively charged, has electronegative balance anion or chlorine or tetrafluoride boron.
In formula (xi), A86And each A89It is each independently selected from monovalent organic groups, hydrogen or inorganic containing hetero atom Group, precondition is A86Mercaptan or phenyl diisopropyl can not be contained.
In formula (xi), A87、A88、A90And A91It is each independently selected from monovalent organic groups, hydrogen or inorganic containing hetero atom Group.
Or, in formula (xi), A88With A90Can be bonded together and form ring structure.Or, A87With A88Can be with key It is combined and forms ring structure.Or, A87With A86Can be bonded together and form ring structure.Or, A86With A91Can be with key It is combined and forms ring structure.Or, A91With A90Can be bonded together and form ring structure.The part of formula (xi) Example include 4226 in table 2,6253,6340,8500,8538,8749,8881,8977,9042,10374,10376, 10377,10379,10380,10381,10390,10450,10451,10452,10454,10455,10456 and 10457.
Or, part can have a formula (xii):
In formula (xii), subscript x is the integer of 1 to 5.Q20Selected from N and P.Dotted line instruction singly-bound or double bond.
In formula (xii), A90、A91、A92、A93、A94And A95It is each independently selected from monovalent organic groups, hydrogen, halogen Atom and inorganic containing heteroatom group, precondition is to work as Q20It is nitrogen and then A time A95 is hydrogen90And A91It not cyclohexyl, and Precondition be A90 and A91 be not DI-tert-butylphenol compounds.
Or, A90With A91Can be bonded together and form ring structure, precondition is when this ring is phospholane ring Time, then A92 and A93 forms phenyl.Or, A91With A92Can be bonded together and form ring structure.Or, A92With A93Permissible Being bonded together and form ring structure, precondition is to work as Q20When being nitrogen, then this ring structure is not indenes.Or, A96With A94Permissible Being bonded together and form ring structure, precondition is to work as Q20Then there is Q when being nitrogen20Ring structure in there are not other miscellaneous Atom.Or, A94With A95Can be bonded together and form ring structure.
In formula (xii), when subscript x is two or more, then A93Two or more entities can be bonded together And form ring structure.The example of the part of formula (xii) include ligand 1 in table 2 0383,10384,10385,10386, 10387,10389,10391,10392,10394,10397,10398,10399,10400,10401,10404,10407 and 10447。
Or, part can have a formula (xiii):
In formula (xiii), subscript x depends on Q21Quantivalence be 0 to 1 integer.Q21Selected from N, O, P and S.
In formula (xiii), A96、A97、A98、A99、A100、A101、A102、A103、A104、A105、A106、A107And A108Each Independently selected from monovalent organic groups, hydrogen, halogen and inorganic containing heteroatom group.Or, A96With A97Can be bonded together and Form ring structure.Or, A99With A100Can be bonded together and form ring structure.Or, A96With A108Can be bonded together And form ring structure.Or, A108With A107Can be bonded together and form ring structure.Or, A107With A106Can be bonded in Form ring structure together.Or, A106With A105Can be bonded together and form ring structure.Or, A105With A104Can be with key Be combined and form ring structure, precondition be this bridge atom be not the N in amido.Or, A104With A103Can be bonded in Form ring structure together.Or, A103With A102Can be bonded together and form ring structure.Or, A102With A101Can be with key It is combined and forms ring structure.The example of the part of formula (xiii) includes 10403 in table 1,10405,10406 and 10446。
Or, part can have a formula (xiv):
In formula (xiv), subscript x and y are the integer of 0 to 5 independently of one another.A111、A110And A112Select independently of one another From monovalent organic groups, hydrogen, halogen atom and inorganic containing heteroatom group.The example of the part of formula (xiv) includes in table 2 3179。
Or, part can have a formula (xv):
In formula (xv), Q22And Q23It is each independently selected from oxygen and sulfur.A115、A116、A117And A118Select independently of one another From monovalent organic groups, hydrogen or inorganic group.
Or, A116With A115Can combine and form ring structure.Or, A118With A119Can combine and form ring structure. The example of the part of formula (xv) includes the part 4570 and 8768 in table 2.
Or, part can have formula (xvi)
In formula (xvi), subscript x and y are the integer of 0 to 4 independently of one another.Q24And Q25Be each independently selected from O and S.Subscript z is the integer of 0 to 1.
In formula (xvi), each A120Independently selected from monovalent organic groups, hydrogen, halogen and inorganic containing hetero atom base Group.
In formula (xvi), A121And A122It is each independently selected from monovalent organic groups, hydrogen and inorganic containing hetero atom base Group.The example of the part of formula (xvi) includes 4548 in table 2 and 6510.
Or, part can have a formula (xvii):
In formula (xvii), Q26Selected from O and S.Q27Selected from N and C.Subscript x is the integer of 0 to 4.A125、A126、A127、 A128And A130It is each independently selected from monovalent organic groups, hydrogen, halogen or inorganic containing heteroatom group.A129Organic selected from unit price Group, hydrogen and inorganic containing heteroatom group, precondition is A128With A129Can combine and form ring structure.Formula (xvii) The example of part includes 10441 in table 2,10444 and 10445.
Or, part can have a formula (xviii):
In formula (xviii), A132、A133And A134It is each independently selected from monovalent organic groups, hydrogen, halogen or inorganic Containing heteroatom group.
In formula (xviii), A131And A135Independently selected from monovalent organic groups, hydrogen and inorganic containing heteroatom group. The example of the part of formula (xviii) includes 10453 in table 2.
Or, part can have a formula (xix):
In formula (xix), each A141, each A142, each A143And each A144Independently selected from monovalent organic radicals Group, hydrogen, halogen or inorganic group.
In formula (xix), A136、A137、A139And A140Independently selected from monovalent organic groups, hydrogen or inorganic group.Logical The example of the part of formula (xix) includes 10150 in table 2.
The neutral form of Exemplary ligands is shown in Table 2.Or, the part for prepared composition (A) can be selected from table 2 In the part of part.
It is commercially available (such as, available commercially from such as following supply herein with useful multiple ligands in upper table Business: U.S. customization chemical company (the American Custom Chemical in San Diego, CA, USA city Corporation, San Diego, Califomia, U.S.A.)；The AlfaAesar company in mountain city, Massachusetts, United States Ward (Alfa Aesar, Ward Hill, Massachusetts, U.S.A.)；The Ai Minta company of Paris, FRA (Ambinter, Paris, France)；The Ai Shang drug research Co., Ltd (Anthem of Connecticut, USA Niu Yindun Pharmaceutical Research LLC, Newington, Connecticut, U.S.A.)；California, USA is holy The Heng Qiao company (ChemBridge Corporation, San Diego, California, U.S.A.) in Di Yage city；The U.S. adds The happy company of Kombi (Combi-Blocks, San Diego, Califomia, U.S.A.) of Diego California, Li Funiya state；Beautiful The lid Le Site company of state Pennsylvania state Mo Lisiweier (Gelest, Inc., Morrisville, Pennsylvania, U.S.A.)；The Yin Teqimu company of California, USA San Pedro (Interchim, Inc., San Pedro, Califomia, U.S.A.)；Belgian Mei Qiao Chemical Co., Ltd. (Maybridge Chemical Co., Ltd., Belgium)；The Princeton biomolecule research company (Princeton of New Jersey Princeton Biomolecular Research, Inc., Princeton, NewJersey, U.S.A.)；St. Louis city Sigma-Aldrich company；Think of spy's Lyme chemical company in Massachusetts, United States Newburyport city；Russia of the U.S. strangles The Ti Xiai u s company (TCI America, Portland, Oregon, U.S.A.) of state, ridge Portland；And U.S. guest sunset method The rad Nuo VWR world, state, Buddhist nun Asia Co., Ltd (VWR International, LLC, Radnor, Pennsylvania, U.S.A.)) and/or can use routine organic chemical synthesis method prepare.
Composition (A) can be by including prepared by the method by above-mentioned part merges with Ni precursor.The method can be optional Further comprising the steps of: before Ni precursor is merged with part, by Ni precursor or part or both be dissolved in solvent.Close The example of suitable solvent has below for those described in composition (S).Or, part can be dissolved in the solvent in container, Solvent can be removed afterwards, then Ni precursor is added to the container accommodating part.The amount of part and Ni precursor is selected Select so that the mol ratio (metal: part ratio) of part and Ni precursor can be 10: 1 to 1: 10 or 2: 1 to 1: 2 or 1: 1 To 1: 4 and or 1: 1 to 1: 2 in the range of.Ni precursor can be merged with part, such as by any suitable means Mix them or vibrate this container in a reservoir.
Make Ni precursor and ligand reaction can by any easily under the conditions of, such as allow before Ni prepared as described above Body and part are reacted a period of time under the room temperature (RT) of-80 DEG C to 200 DEG C or 25 DEG C, are come by heating or combinations thereof Carry out.Can such as heat higher than 25 DEG C to 200 DEG C or at being higher than 25 DEG C to 75 DEG C.Heating can be by any facility Means, such as carried out by heating mantle, heating coil or container is placed in baking oven.Complex reaction temperature depends on including Selected concrete Ni precursor and the reactivity of part and metal: part ratio at interior many factors, but, temperature is permissible In the range of 25 DEG C to 200 DEG C or 25 DEG C to 75 DEG C.The complex reaction time is depended on including selected reaction temperature Many factors, but, the complex reaction time generally can be at 1 second (s) to 48 hour (h) or 1 minute (min) to 30 hours (h) and or 45 minutes to 15 hours in the range of.Sequentially part can be merged with Ni precursor and heat.Or, permissible Part merged with Ni precursor simultaneously and heat.
The method of the catalysis active reaction product of prepared composition (A) may also include activation reaction prepared as described above and produces Thing.Activation reaction product can be by merging the metal reduced in Ni-ligand complex by above-mentioned product with reducing agent The form oxidation state of atom is carried out.The example of the reducing agent that can merge with product includes the amalgam of alkali-metal；Hydrogen, gold Belong to hydride, such as lithium aluminium hydride (LiAlH4) or sodium naphthalene；(it is the most all right for silyl hydride It is all or part of silane crosslinker hereinafter described)；Or metallic boron hydrides, such as sodium triethylborohydride (NaEt3BH)、 Lithium triethylborohydride (LiEt3Or sodium borohydride (NaBH BH)4).Suitably reducing agent includes that Chem.Rev. (" (comment by chemistry Opinion) "), those described in 1996,96,877-910.
Or, can be by including that the method that above-mentioned product merges with ion activation agent activates above-mentioned reaction produces Thing.The example of the ion activation agent in this method includes carborane, such as Li+ [CB11H6Br6]-、Li+[CB9H5Br5]-、 Li+[CB11H10Br2]-and Li+ [CB9H8Br2]-、NH4+[CB11H6Br6]-、NH4+[CB9H5Br5]-、NH4+ [CB11H10Br2]-、NH4+[CB9H8Br2]-、Na+[CB11H6Br6]-、Na+[CB9H5Br5]-、Na+[CB11H10Br2]-and Na+ [CB9H8Br2]-；Or metal borate, such as four (pentafluorophenyl group) Lithium biborate (LiBArF), four (3,5-trifluoromethyl) phenylboric acid Lithium, four (3,5-trifluoromethyl) phenylboric acid sodium or their mixture.
Or, can be above-mentioned the most original by including activating the method that above-mentioned product merges with neutral activator Thing.The example of the neutral activator in this method includes three (pentafluorophenyl group) borines and three (pentafluorophenyl group) alkyl (tris(pentafluorophenyl)akylane)。
The method of the catalysis active reaction product of prepared composition (A) adds solvent after can being optionally additionally included in reaction.Properly The example of solvent have below for those described in composition (S).Or, the method can the most also include removing byproduct of reaction And/or solvent is (if there is solvent (such as, for promoting Ni precursor and part before complex reaction or the merging of period) Words).By-product includes such as H-A (wherein A is as above defined in formula (i)) or by when part is with Ni precursors reaction Replaceable substituent group reacts and departs from any material produced by Ni precursor.Can be by any means easily, such as Under heating or carry out under vacuo stripping or distill and/or filter, crystallize or combinations thereof is to remove by-product.Gained The Ni-ligand complex of separation be used as the catalysis active reaction product of composition (A).
Or, byproduct of reaction is not being removed by catalysis active reaction product as composition (A) is front.Such as, can incite somebody to action Solvent removal or not by solvent removal and make part and Ni precursor in the case of carrying out activating or not activating as mentioned above Reaction, and the product of gained (can be comprised Ni-ligand complex and byproduct of reaction and optional solvent or dilution Agent) it is used as composition (A).Being not bound by theory, it is believed that in addition to Ni-ligand complex, by-product can also serve as Catalyst for addition reaction of hydrogen and silicon, or serve as promoter or activator.Therefore, product can catalyzing addition reaction of silicon with hydrogen.
Compositions can be containing a kind of single catalyst.Or, said composition may be embodied in and composition (A) is described above Two or more catalyst, wherein these two or more catalyst are at the selection of at least one character such as part, precursor Selection, metal: in part ratio and formula (i), the definition aspect of group A is different.Said composition can not be urged by platiniferous Agent.Or, said composition can be without conventional metallic catalyst.Or, said composition can be without in addition to composition (A) Can any Ni compound of hydrosilylation of unsaturated group on catalyst component (B).Or, said composition is permissible Without the catalyst for addition reaction of hydrogen and silicon in addition to composition (A).Or, said composition can be without the energy in addition to composition (A) Any composition of the hydrosilylation of the unsaturated group on enough catalyst components (B).
Composition (A) is present in compositions with catalytically effective amount.Definite amount depends on many factors, including composition (A) Reactivity, the type of composition (B) and amount and the type of any other composition (if present) and amount.But, with group The gross weight meter of all the components in compound, in compositions, the amount of composition (A) can be at 1 PPM (ppm) to 5% or 0.1% To 2% and or 1ppm to 1% in the range of.
Composition (B) is aliphatic series unsaturated compound, and described aliphatic series unsaturated compound average per molecule has one or many The individual unsaturated organic group of aliphatic series that can carry out hydrosilylation.Or, composition (B) per molecule can averagely have two or The unsaturated organic group of more aliphatic series.The unsaturated organic group of aliphatic series can be thiazolinyl, and the example of described thiazolinyl has but is not limited to Vinyl, pi-allyl, acrylic, cyclobutenyl and hexenyl.Unsaturated organic group can be alkynyl, the example of described alkynyl have but It is not limited to acetenyl, propinyl and butynyl.
The composition (B) of said composition can be unsaturated hydrocarbons, and wherein unsaturated group can come anti-by hydrosilylation Should.Composition (B) can be monomer.Such as, it is adaptable to the aliphatic unsaturated organic compound of composition (B) includes but not limited to alkene, Such as ethylene, propylene, 1-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene；Halogenated olefins, such as allyl chloride；Diene, such as two Vinyl benzene, butadiene, 1,5-hexadiene and monovinylacetylene；Cyclenes, such as cyclohexene and cycloheptene；And alkynes, such as second Alkynes, propine and 1-hexin.
Oxygen-containing aliphatically unsaturated compound can also be used for composition (B), wherein unsaturated group be ethylenic not Saturated group, such as vinylcyclohexyl epoxide, allyl glycidyl ether, methyl vinyl ether, divinyl ether, benzene Base vinyl ethers, the mono allyl ether of ethylene glycol, allyl aldehyde, methyl vinyl ketone, phenyl vinyl ketone, acrylic acid, methyl-prop Olefin(e) acid, acrylic acid methyl ester., allyl acrylate, methyl methacrylate, allyl methacrylate, vinyl acetic acid, acetic acid Vinyl acetate and linolenic acid.
In ring, the heterocyclic compound (such as dihydrofuran and dihydropyran) containing aliphatic series unsaturated group is also suitable and is made Divide (B).Unsaturated compound (such as acrylonitrile, NVP, alkyl cyanide, nitroethylene) containing nitrogen substituent group is also It is suitable as composition (B).
Or, the composition (B) of compositions comprises polymer.Composition (B) can comprise average per molecule and have one or many The base polymer of the individual unsaturated organic group of aliphatic series that can carry out hydrosilylation.Composition (B) can comprise above-mentioned many The polymer (such as copolymer or trimer) of kind of compound, precondition is to there is at least one can to carry out Si-H addition reaction anti- The aliphatic unsaturated group answered.Example includes derived from having the olefinic monomer of 2 to 20 carbon atoms and to have 4 to 20 carbon former The polymer of the diene of son；The polymer of monoolefine, isomonoolefin and vi-ny l aromatic monomers, as having 2 to 20 carbon-based groups Monoolefine, there is the isomonoolefin of 4 to 20 carbon-based groups and include styrene, to ring-alkylated styrenes, p-methylstyrene Polymer at interior vi-ny l aromatic monomers.Or, these compounds can be poly-(diene).Major part is derived from diene Polymer generally contains unsaturated ethylenic units on main chain or side chain.Representative example includes polybutadiene, poly-isoamyl two Alkene, polytetramethylene alkene, poly-(alkyl-butenylidene) (wherein alkyl includes the alkyl with 1 to 20 carbon atom), poly-(phenyl-Asia Butylene), poly-inferior pentenyl, natural rubber (polyisoprene of a kind of form)；And butyl rubber (isobutene. and isoprene Copolymer).
Or, composition (B) can comprise the halogenated olefin polymer with aliphatic unsaturated group.There is aliphatic series unsaturated The representative example of the halogenated olefin polymer of group includes by carrying out the copolymer of isomonoolefin with p-methylstyrene Bromination is to introduce polymer, halogenated polybutadiene, halogenated polyisobutylene, poly-(2-chloro-1,3-fourth two produced by benzyl halogen Alkene), polychlorobutadiene (85% is trans), poly-(1-chloro-1-butenylidene) () and chlorosulfonated polyethylene.
Or, composition (B) can comprise containing other compounds above-mentioned (such as vinyl Ether group, acrylate group, methyl-prop Enoate group and epoxy-functional) polymer.
Or, composition (B) can comprise the silane with aliphatic unsaturated group.Or, this silane can have formula R35 xxSiR36 (4-xx), wherein subscript xx is integer and or the integer 1 of 1 to 4 or 1 to 3.R35It it is the unsaturated organic group of aliphatic series Group, and R36Selected from H, halogen atom and monovalent organic groups.
Or, composition (B) can comprise and has containing the aliphatic series straight chain of unsaturated group, side chain, ring-type or resin structure Siliceous base polymer.Or, base polymer can have straight chain and/or branched structure.Or, base polymer can have tree Fat structure.Base polymer can be homopolymer or copolymer.Composition (B) can be a kind of base polymer.Or, composition (B) can Comprise two or more base polymers, the two or more kinds of base polymer in following character at least one be Different: structure, viscosity, mean molecule quantity, siloxane unit and order.The unsaturated organic group of aliphatic series in base polymer Can be located at both terminal position, side chain positions or terminal position and side chain positions.
In the base polymer of composition (B), the organic group of remaining silicon bonding can be the list without aliphatic series unsaturated group Valency organic group.The example of univalence hydrocarbyl includes but not limited to alkyl, as Me, Et, Pr, Bu, amyl group, hexyl, heptyl, octyl group, Decyl, dodecyl, undecyl and octadecyl cycloalkyl, such as cyclopenta and cyclohexyl；Aryl, such as Ph, tolyl, diformazan Phenyl and naphthyl；And aralkyl, such as benzyl, 1-phenethyl and 2-phenethyl.The example of monovalent halogenated alkyl includes but does not limits In: chlorination alkyl, such as chloromethyl and chloropropyl；Fluorinated alkyl, as methyl fluoride, 2-fluoropropyl, 3,3,3-trifluoro propyls, 4,4,4- TriRuorobutyl, 4,4,4,3,3-five fluorine butyl, 5,5,5,4,4,3,3-seven fluorine amyl groups, 6,6,6,5,5,4,4,3,3-nine fluorine hexyls With 8,8,8,7,7-five fluorine octyl groups；Chlorination cycloalkyl, such as 2,2-dichloro cyclopropyl, 2,3-dichloro cyclopenta；And fluorination cycloalkanes Base, such as 2,2-difluorocyclopropyl, 2,3-difluoro cyclobutyl, 3,4-difiuorocyclohexyl and 3,4-bis-fluoro-5-methylcycloheptyl.Other The example of monovalent organic groups includes but not limited to: the alkyl replaced by oxygen atom such as glycidyl-oxyalkyl, and former by nitrogen Son substituted alkyl such as aminoalkyl and cyano functional group such as cyanoethyl and cyanogen propyl group.
Composition (B) can comprise the polydiorganosiloxanepolyurea of following formula
Formula (I): R1 2R2SiO(R1 2SiO)a(R1R2SiO)bSiR1 2R2,
Formula (II): R1 3SiO(R1 2SiO)c(R1R2SiO)dSiR1 3,
Or combinations thereof.
In formula (I) and (II), each R1Independently be hydrogen atom or the monovalent organic radicals without aliphatic series unsaturated group Group and each R2Independently be the unsaturated organic group of aliphatic series, its example is those described above.Subscript a can be 0 or Positive number.Or, subscript a has the meansigma methods of at least 2.Or, subscript a can have the value in the range of 2 to 2000.Subscript b is permissible It is 0 or positive number.Or, subscript b can have the meansigma methods in the range of 0 to 2000.Subscript c can be 0 or positive number.Or under, Mark c can have the meansigma methods in the range of 0 to 2000.Subscript d has the meansigma methods of at least 2.Or, subscript d can have 2 to Meansigma methods in the range of 2000.R1Suitable monovalent organic groups for as described above for described in composition (B).Or, each R1It is single Valency alkyl, its example has alkyl such as Me, and aryl such as Ph.Each R2Independently be as described above for the aliphatic series described in composition (B) Unsaturated monovalent organic groups.Or, R2Example have thiazolinyl, such as vinyl, pi-allyl, cyclobutenyl and hexenyl；And alkynes Base, such as acetenyl and propinyl.
Composition (B) can comprise polydiorganosiloxanepolyurea, as
I) polydimethylsiloxane of dimethylvinylsiloxy end-blocking,
Ii) poly-(dimethyl siloxane/methyl vinyl silicone) of dimethylvinylsiloxy end-blocking,
Iii) Polymethyl methacrylate of dimethylvinylsiloxy end-blocking,
Iv) poly-(dimethyl siloxane/methyl vinyl silicone) of trimethylsiloxy end-blocking,
V) Polymethyl methacrylate of trimethylsiloxy end-blocking,
Vi) poly-(dimethyl siloxane/methyl vinyl silicone) of dimethylvinylsiloxy end-blocking,
Vii) poly-(dimethyl siloxane/methyl phenyl siloxane) of dimethylvinylsiloxy end-blocking,
Viii) poly-(dimethyl siloxane/diphenyl siloxane) of dimethylvinylsiloxy end-blocking,
Ix) phenyl, methyl, the polydimethylsiloxane of vinyl-siloxy end-blocking,
X) polydimethylsiloxane of dimethyhexenes base siloxy end-blocking,
Xi) poly-(dimethyl siloxane/methylhexenylsiloxane) of dimethyhexenes base siloxy end-blocking,
Xii) the poly-methylhexenylsiloxane of dimethyhexenes base siloxy end-blocking,
Xiii) poly-(dimethyl siloxane/methylhexenylsiloxane) of trimethylsiloxy end-blocking,
Xiv) the poly-methylhexenylsiloxane of trimethylsiloxy end-blocking,
Xv) poly-(dimethyl siloxane/methylhexenylsiloxane) of dimethyhexenes base siloxy end-blocking,
Xvi) poly-(dimethyl siloxane/methylhexenylsiloxane) of dimethylvinylsiloxy end-blocking,
Xvii) combinations thereof.
It is suitable for use as the preparation method of the polydiorganosiloxane fluid of composition (B), such as, corresponding organo-halogen-silane Hydrolyze and be condensed or the equilibrating of ring-type polydiorganosiloxanepolyurea, be well known in the art.
In addition to above-mentioned polydiorganosiloxanepolyurea or as the replacement of above-mentioned polydiorganosiloxanepolyurea, composition (B) also can wrap Resinous, as substantially by R3 3SiO1/2Unit and SiO4/2Unit composition MQ resin, substantially by R3SiO3/2Unit and R3 2SiO2/2Unit composition TD resin, substantially by R3 3SiO1/2Unit and R3SiO3/2Unit composition MT resin, substantially by R3 3SiO1/2Unit, R3SiO3/2Unit and R3 2SiO2/2The MTD resin of unit composition or combinations thereof.
Each R3For monovalent organic groups, its example is for above in relation to those described in composition (B).Or, by R3Represent Monovalent organic groups can have 1 to 20 carbon atom.Or, R3The example of monovalent organic groups include but not limited to monovalent hydrocarbon Base and monovalent halogenated alkyl.
Resin can the unsaturated organic group of aliphatic series containing average 3 moles of % to 30 mole of % or 0.1 mole of % rub to 30 The unsaturated organic group of aliphatic series of you % or 0.1 mole of % to 5 mole of % or 3 moles of % to 100 mole of %.Aliphatic series is unsaturated Organic group can be thiazolinyl, alkynyl or combinations thereof.In resin, mole % of the unsaturated organic group of aliphatic series is to contain in resin The molal quantity of the siloxane unit of unsaturated group is multiplied by 100 with the ratio of the total mole number of siloxane unit in resin.
The preparation method of resin is well known in the art.For example, it is possible to by using at least one to contain the end-capping reagent of thiazolinyl The resin copolymer that place's reason Daudt et al. described silica hydrosol end blocking method generates prepares resin.Daudt etc. Method described in people is disclosed in United States Patent (USP) 2,676,182.
The method of Daudt et al. relate to making silica hydrosol in acid condition with hydrolyzable three organosilans (such as trim,ethylchlorosilane), siloxanes (such as hexamethyl disiloxane) or their mixture reaction, and reclaim there is M unit Copolymer with Q unit.The copolymer of gained usually contains the hydroxyl of 2 to 5 weight %.
This resin (generally comprising the hydroxyl of the bonding of the silicon less than 2%) can be prepared via a method which: makes Daudt et al. institute The product stated and the end-capping reagent containing unsaturated organic group and the end-capping reagent without aliphatic series unsaturated group are be enough to finally producing Thing provides the quantitative response of the unsaturated organic group of 3 to 30 moles of %.The example of end-capping reagent includes but not limited to silazane, silicon Oxygen alkane and silane.Suitably end-capping reagent is to it known in the art, and be illustrated in United States Patent (USP) 4,584,355,4, and 591,622 Hes In 4,585,836.The mixture of single end-capping reagent or this type of reagent may be used for preparing described resin.
Or, composition (B) can comprise the siliceous base polymer in addition to above-mentioned polysiloxane.Such as, it is adaptable to Other compounds of composition (B) include silazane and/or containing by the hydrocarbon of such as alkylidene or polyalkylene or arlydene etc The polymeric material of the silicon atom that base is bonded together.The organic compound of the Si modification that can be used as composition (B) include having to The organic polymer of a few silicon atom connecting into silane or siloxanes segment.Siliceous unit can be containing aliphatic series unsaturated group Roll into a ball and can be connected on the terminal position on organic polymer chain and/or side chain positions or connect into copolymer.For The example of other representational silicon modified organic polymers of composition (B) has but is not limited to thiazolinyl siloxy official and can be polymerized Thing, such as vinyl silane epoxide organic polymer, pi-allyl siloxy organic polymer and hexenylsiloxy Organic polymer and siloxanes organic-block co-polymer.The example of silane-modified organic polymer is derived from alkene, different Monoolefine, diene, oxirane or expoxy propane and there is the silicyl of vi-ny l aromatic monomers of 2 to 20 carbon atoms Fluidized polymer, such as the silane grafted copolymers of isomonoolefin Yu vi-ny l aromatic monomers.
The example of the organic polymer of Si modification mentioned above includes the poly-(dimethyl that vinyl silane epoxide blocks Siloxanes/alkyl) copolymer or hexenylsiloxy end-blocking poly-(dimethyl siloxane/alkyl) copolymer；Vinyl Poly-(dimethyl siloxane/polyoxyalkylene) block copolymer of siloxy end-blocking or gathering of hexenylsiloxy end-blocking (dimethyl siloxane/polyoxyalkylene) block copolymer；The polyisobutylene of alkenyloxy group dimethyl silane epoxide end-blocking and alkene oxygen Polydimethylsiloxane/the polyisobutylene block copolymer of base dimethyl silane epoxide end-blocking.It is applicable to the chemical combination of composition (B) The example of thing can see in such as WO2003/093369.
In compositions, the amount of composition (B) depends on the many factors including the following: the product of compositions Desired form, the amount of aliphatic unsaturated group of composition (B) and hydrosilylation, the type of composition (A) and amount and The content of the hydrogen atom of the silicon bonding of composition (B) and/or composition (C).But, in terms of the weight of all the components in compositions, become The amount dividing (B) can be in the range of 0.1% to 99.9%.
Composition (C) in compositions is the hydrogen that SiH functional compound, i.e. average per molecule have one or more silicon bonding The compound of atom.Composition (C) can comprise silane and/or organic hydrogen-silicon compound.Or, composition (C) can average per molecule There is the hydrogen atom of at least two silicon bonding.In compositions the amount of composition (C) depend on including the following multiple because of Element: the character of the product of the SiH content of composition (C), the unsaturated group mass contg of composition (B) and required compositions, But, the amount of composition (C) can be enough to provide the SiH base in the composition (C) in the range of 0.3: 1 to 5: 1 or 0.1: 10 to 10: 1 The mol ratio (being commonly called SiH: Vi ratio) of group's organic group unsaturated with the aliphatic series in composition (B).Composition (C) can have Monomer or paradigmatic structure.When composition (C) has paradigmatic structure, this paradigmatic structure can be straight chain, side chain, ring-type or resin knot Structure.When composition (C) is polymer, then composition (C) can be homopolymer or copolymer.In composition (C), the hydrogen atom of silicon bonding can To be positioned at both terminal position, side chain positions or terminal position and side chain positions.Composition (C) can be a kind of SiH functional compound. Or, composition (C) can comprise the combination of two or more SiH functional compounds.Composition (C) can be that two or more are organic Hydrogen polysiloxanes, the two or more kinds of organic hydrogen polysiloxanes in following character at least one be different: structure, Mean molecule quantity, viscosity, siloxane unit and sequence.
Composition (C) can contained R4 eSiHfSilane, wherein subscript e is 0,1,2 or 3；Subscript f is 1,2,3 or 4, premise Condition be (e+f) sum be 4.Each R4Independently be halogen atom or monovalent organic groups.R4The example of suitable halogen atom There are chlorine, fluorine, bromine and iodine；Or chlorine.R4Suitable monovalent organic groups include but not limited to univalence hydrocarbyl and monovalent halogenated alkyl. Univalence hydrocarbyl includes but not limited to alkyl, as Me, Et, Pr, Bu, amyl group, hexyl, heptyl, octyl group, decyl, dodecyl, 11 Alkyl and octadecyl；Cycloalkyl, such as cyclopenta and cyclohexyl；Aryl, such as Ph, tolyl, xylyl and naphthyl；And virtue Alkyl, such as benzyl, 1-phenethyl and 2-phenethyl.The example of monovalent halogenated alkyl includes but not limited to: chlorination alkyl, such as chloromethane Base and chloropropyl；Fluorinated alkyl, as methyl fluoride, 2-fluoropropyl, 3,3,3-trifluoro propyls, 4,4,4-triRuorobutyl, 4,4,4,3, 3-five fluorine butyl, 5,5,5,4,4,3,3-seven fluorine amyl groups, 6,6,6,5,5,4,4,3,3-nine fluorine hexyls and 8,8,8,7,7-five fluorine Octyl group；Chlorination cycloalkyl, such as 2,2-dichloro cyclopropyl, 2,3-dichloro cyclopenta；And fluorinated cycloalkyl, such as 2,2-difluoro ring third Base, 2,3-difluoro cyclobutyl, 3,4-difiuorocyclohexyl and 3,4-bis-fluoro-5-methylcycloheptyl.The example of other monovalent organic groups Son includes but not limited to: the alkyl replaced by oxygen atom such as glycidyl-oxyalkyl, and alkoxyl such as methoxyl group, ethyoxyl, Propoxyl group and butoxy；With the alkyl such as aminoalkyl replaced by nitrogen-atoms；And cyano functional group such as cyanoethyl and cyanogen propyl group. The example of the suitable silane of composition (C) has trichlorosilane (HSiCl3)、Me2HSiCl or MeHSi (OMe)2。
Or, composition (C) organic hydrogen-silicon compound can comprise the poly-organohydrogensiloxanes with siloxane unit, described Siloxane unit includes but not limited to HR5 2SiO1/2、R5 3SiO1/2、HR5SiO2/2、R5 2SiO2/2、R5SiO3/2、HSiO3/2And SiO4/2 Unit.In previously described formula, each R5Independently selected from the above-mentioned monovalent organic groups without aliphatic series unsaturated group.
Composition (C) can comprise the poly-organohydrogensiloxanes of following formula:
Formula (III): R5 3SiO(R5 2SiO)g(R5HSiO)hSiR5 3,
Formula (IV): R5 2HSiO(R5 2SiO)i(R5HSiO)jSiR5 2H, or
Combinations thereof.
In upper formula (III) and (IV), subscript g has the meansigma methods in the range of 0 to 2000, subscript h have 2 to Meansigma methods in the range of 2000, subscript i has the meansigma methods in the range of 0 to 2000, and subscript j has at 0 to 2000 model Enclose interior meansigma methods.Each R5Independently be above-mentioned monovalent organic groups.
The example of the poly-organohydrogensiloxanes of composition (C) has:
A) polydimethylsiloxane of dimethylhydrogensiloxy end-blocking,
B) poly-(dimethyl siloxane/methyl hydrogen siloxane) of dimethylhydrogensiloxy end-blocking,
C) polymethyl hydrogen siloxane of dimethylhydrogensiloxy end-blocking,
D) poly-(dimethyl siloxane/methyl hydrogen siloxane) of trimethylsiloxy end-blocking,
E) polymethyl hydrogen siloxane of trimethylsiloxy end-blocking,
F) substantially by H (CH3)2SiO1/2Unit and SiO4/2The resin of unit composition, and
G) combinations thereof.
It is suitable for use as the straight chain of composition (C), side chain and the preparation method of ring-type organic hydrogen polysiloxanes, such as halogenated organic The hydrolysis of silane and condensation, be well known in the art.It is suitable for use as the preparation method of the organic hydrogen polysiloxanes resin of composition (C) Also, known to being, it is in United States Patent (USP) 5, and 310,843,4,370,358 and 4, carry out example in 707,531.
Or, the organic hydrogen-silicon compound of composition (C) can comprise (V) compound:
The most each R29Independently selected from hydrogen atom and the monovalent organic groups comprising 1 to 20 member atoms, subscript k is It is worthInteger in the range of 0 to 18, subscript m is for being worth 0Integer in the range of 19, k+m for value 3 to 20 or 3 to Integer in the range of 40.Each R30Independently selected from the monovalent organic groups as described in upper part, halogen atom or silica Alkane unit.Or, each R30It is independently selected from following functional group: halogen atom, ether, alkoxyl, alkoxyether groups, acyl Base, epoxy radicals, amino, silicyl or-Z-R31Group, the most each Z is independently selected from oxygen atom and to comprise 2 to 20 carbon former The bivalent hydrocarbon radical of son, each R31Group is independently selected from-BR29 u R32 2-u、-Si R29 v R32 3-vOr the base described with formula (VI) Group:
(R32 3-nR29 nSiO1/2)w(R32 2-oR29 oSiO2/2)x(R32 1-pR29 pSiO3/2)v(SiO4/2)z(CR29 qR32 1-
q)aa(CR29 rR32 2-r)bb(O(CR29 sR32 2-s)cc(CR29 tR32 3-t)dd
Wherein B refers to boron, each R29As described above, w+x+y+z+aa+bb+cc+dd sum is at least 2, and subscript n is value Integer in the range of 0 to 3, subscript o is value integer in the range of 0 to 2, and subscript p is value integer in the range of 0 to 1, under Mark q is value integer in the range of 0 to 1, and subscript r is value integer in the range of 0 to 2, and subscript s is that value is in the range of 0 to 2 Integer, subscript t is value integer in the range of 0 to 3, and subscript u is value integer in the range of 0 to 2, and subscript v is that value is 0 to 3 In the range of integer, each R32Be independently selected from following functional group: halogen atom, ether, alkoxyl, alkoxyether groups, Acyl group, epoxy radicals, amino, silicyl or Z-G group, wherein Z is as described above, and each G is the ring silicon described with formula (VII) Oxygen alkane:
Wherein R29And R30As described above, subscript ee is 1, and subscript ff is value integer in the range of 0 to 18, subscript gg Being value integer in the range of 0 to 18, ff+gg is value integer in the range of 2 to 20, and precondition is in formula (VII), R32 Being replaced by Z group for one in group, described Z group makes R31Group bonding is on the cyclosiloxane of formula (VII), and premise Condition is also if aa+bb+cc+dd > 0, then w+x+y+z > 0.
These organic hydrogen-silicon compounds are commercially available and includeSL2 cross-linking agent andSL12 cross-linking agent, both of which is available commercially from the Dow Corning Corporation (DoW of Michigan, USA Midland Coming Corporation, Midland, Michigan, U.S.A).Above-mentioned organic hydrogen-silicon compound and their preparation side Method is illustrated in WO2003/093349 and WO2003/093369.Exemplary organic hydrogen-silicon compound can have a formula:
The most every Individual R33Independently selected from hydrogen atom and monovalent organic groups；Each R34Independently selected from hydrogen atom, monovalent organic groups and formulaGroup；Subscript hh is the integer of value at least 1；Subscript jj is that value is at least The integer of 1；And subscript ii be minima be the integer of 0.In this formula, R33At least one entity be hydrogen atom.It is suitable for In R33And/or R34The example of monovalent organic groups have above for R29Those described groups.
In compositions composition (C) definitely measure certainly in the many factors including the following: the reaction of composition (A) Property, the type of composition (B) and amount, composition (B) whether contain the hydrogen atom of silicon bonding, and any other composition is (except composition (C) beyond) type of (if present) and amount.But, in terms of the gross weight of all the components in compositions, compositions becomes The amount of point (C) can 0% to 25% or 0.1% to 15% and or 1% to 5% in the range of.
Composition (D) is spacer.Spacer can include organic filler, inorganic particulate or combinations thereof.Spacer can Be heat conduction, conduction or the two have concurrently.Spacer can have required granularity, and such as, granularity can be at 25 microns of (μ M) in the range of 125 μm.Spacer can comprise monodispersed globule, such as glass or polymer (e.g., polystyrene) globule. Spacer can comprise heat filling, such as, aluminium oxide, aluminium nitride, atomized metal pow der, boron nitride, copper and silver.Composition (D) Amount depends on many factors, including particle size distribution, will apply during the use of compositions or cured product prepared therefrom Pressure, use during temperature and compositions or the desired thickness of cured product prepared therefrom.But, compositions Can be containing the amount of the composition (D) in the range of 0.05% to 2% or 0.1% to 1%.
Composition (E) is extender and/or plasticizer.The extender of the polysiloxane comprising nonfunctionalized can be used for group In compound.Such as, the polysiloxane of nonfunctionalized can be with contained R6 28iO2/2Difunctional unit and Shi R7 3SiR28- Terminal units, the most each R6With each R7Independently be monovalent organic groups, such as univalence hydrocarbyl, its example has: alkyl, such as first Base, ethyl, propyl group and butyl；Thiazolinyl, such as vinyl, pi-allyl and hexenyl；Aryl, such as Ph, tolyl, xylyl and naphthalene Base；And aralkyl, such as phenethyl；And R28For oxygen atom or the silicon atom of terminal units is connected with another silicon atom two Valency group.R28Divalent linker can be divalent organic group, organosilicon organic group or bivalent hydrocarbon radical and bivalence silica The combination of groups.Or, each R28Can be independently selected from oxygen atom and bivalent hydrocarbon radical.Or, each R28It can be oxygen atom. Or, each R28Can be bivalent hydrocarbon radical, its example has: alkylidene, such as ethylidene, propylidene, butylidene or hexylidene；Arlydene Such as phenylene, or alkyl arylene is such as:
OrOr, R28One Entity can be oxygen atom, and R28A different entities be bivalent hydrocarbon radical.The polysiloxane of nonfunctionalized be this area Know, and commercially available.The example of the polysiloxane of the nonfunctionalized being suitable for has (but not limited to) poly dimethyl silicon Oxygen alkane.Such polydimethylsiloxane includes DOW200 fluids, it can be from Michigan, USA Midland The Dow Corning Corporation in city is commercially available, and can have 50cSt to 100,000cSt or 50cSt to 50,000cSt or 12, Viscosity in the range of 500cSt to 60,000cSt.
Organic plasticizers can be also used in addition to the polysiloxane extender of above-mentioned nonfunctionalized, or permissible Organic plasticizers is used to replace above-mentioned nonfunctionalized polysiloxane extender.Organic plasticizers is to it known in the art, also And it is commercially available.Organic plasticizers can comprise phthalic acid ester, carboxylate, carboxylate, adipate ester or combinations thereof. Organic plasticizers can be selected from: double (2-ethylhexyl) ester of p-phthalic acid；Double (2-ethylhexyl) ester of Isosorbide-5-Nitrae-phthalic acid；1, 4-phthalic acid 2-ethylhexyl methyl ester；1,2-cyclohexane cyclohexanedimethanodibasic two nonyl ester, side chain and straight chain；Double (the 2-of phthalic acid Propylheptyl) ester；Diisononyl adipate；And combinations thereof.
Organic plasticizers can have at least one formula by average per moleculeGroup, wherein R8Represent hydrogen atom or Monovalent organic groups.Or, R8Side chain or linear monovalent hydrocarbon radical can be represented.Monovalent organic groups can be side chain or straight chain list Valency alkyl, as having the alkyl of 4 to 15 carbon atoms or 9 to 12 carbon atoms.Be suitable for plasticizer be selected from adipate ester, Carboxylate, phthalic acid ester and combinations thereof.
Or, organic plasticizers can have the above formula base of at least two and the carbon atom bonding in cyclic hydrocarbon with average per molecule Group.Organic plasticizers can have a below general formula:
In the formula, group Z represents have 3 or more carbon atom or the cyclic hydrocarbon radical of 3 to 15 carbon atoms.Subscript k Can have the value in the range of 1 to 12.Group Z can be saturated or aromatics.Each R10Independently be hydrogen atom or side chain Or linear monovalent organic group.R9Monovalent organic groups can be alkyl, such as Me, Et or Bu.Or, R10Monovalent organic radicals Group can Shi Zhi functional group.Each R9Independently be side chain or linear monovalent hydrocarbon radical, as having the alkyl of 4 to 15 carbon atoms.
The organic plasticizers being suitable for is to it known in the art, and commercially available.Plasticizer can comprise phthalic acid Ester, such as: bialkyl ortho phthalate, such as dibutyl phthalate (EastmanTMDBP plasticizer), phthalic acid two Heptyl ester, phthalic acid two (2-ethylhexyl) ester or diisooctyl phthalate (DIDP), double (the 2-propyl group of phthalic acid Heptyl) ester (BASFDPHP), phthalic acid two (2-ethylhexyl) ester (EastmanTMDOP plasticizer), adjacent Dimethyl phthalate (EastmanTMDMP plasticizer)；Diethyl phthalate (EastmanTMDMP plasticizer)；Adjacent benzene two Formic acid butyl benzyl and double (2-ethylhexyl) ester (Eastman of p-phthalic acidTM425 plasticizers)；Dicarboxylic ester, such as O, O-benzyl Base, C7-C9 straight chain and branched alkyl-1,2-phthalic acid ester (FCrro261A), 1,2,4-benzene tricarboxylics Acid (BASFTOTM-I), double (2-ethylhexyl) ester (Eastman of Isosorbide-5-Nitrae-phthalic acidTM168 plasticizers)；O,O- (2-ethylhexyl), methyl isophthalic acid, 4-benzene dicarboxylic acid esters；Side chain and straight chain 1,2-cyclohexane cyclohexanedimethanodibasic two nonyl ester (BASF Hexamo1l*DINCH)；Diisononyl adipate；Trimellitate, such as trioctyl trimellitate (TOTM) (EastmanTMMTOTM plasticising Agent)；Double (2 ethyl hexanoic acid) triethyleneglycol ester (EastmanTMTEG-EH plasticizer)；Glyceryl triacetate (EastmanTMTriacetic acid Glyceride)；Non-aromatic dibasic acid ester, such as dioctyl adipate, double (2-ethylhexyl) ester (Eastman of adipic acidTMDOA plasticising Agent and EastmanTMDOA plasticizer, Kosher), di-2-ethylhexyl adipate (BASFDOA), decanedioic acid Dioctyl ester, dibutyl sebacate and DID Su；Aliphatic (acid) ester, such as butyl oleate and acetyl group methyl ricinoleate；Phosphoric acid Ester, such as tricresyl phosphate and tributyl phosphate；Chlorinated paraffin；Hydrocarbon ils, such as alkyl biphenyl and partially hydrogenated terphenyl；Technique Oil；Epoxy plasticizer, such as epoxidised soybean oil and epoxystearic acid benzene methyl；Three (2-ethylhexyl) ester；Fatty acid ester；And Combinations thereof.The example of other suitable plasticizers and commercial source thereof includes BASF652 Hes Eastman168XtremeTMPlasticizer.
Or, polymeric plasticizer can be used.The example of polymeric plasticizer includes by making second by means of various methods The alkenyl polymer that thiazolinyl or allyl monomer are polymerized and obtain；Poly alkylene glycol ester, such as diethylene glycol dibenzoate, three sweet Alcohol dibenzoate and pentaerythritol ester；By binary acid (such as decanedioic acid, adipic acid, Azelaic Acid and phthalic acid) and dihydroxylic alcohols The polyester plasticizer that (such as ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., propylene glycol and dipropylene glycol) obtains；Polyethers is the least including respectively having In the polyether polyol of the molecular weight of 500, such as Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol；Polystyrene, such as polyphenyl Ethylene and poly alpha methylstyrene；With polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile and polychlorobutadiene.
Can each be used alone above for the polysiloxane extender described in composition (E) and organic plasticizers or with Both it or more person combining form use.Low-molecular-weight organic plasticizers and higher molecular weight polymer plasticizer can be combined Use.The definite amount of composition (E) in compositions will depend upon which many factors, including the institute of compositions He its cured product Need final use.But, in terms of the gross weight of all the components in compositions, the amount of composition (E) can be in the scope of 0.1% to 10% In.
Composition (F) is filler.Filler can comprise enhancement filler, increase filling property filler, conductive filler or combinations thereof. Such as, compositions can the most also comprise composition (f1) enhancement filler, in terms of the weight of compositions, its in the presence of permissible The amount of 0.1% to 95% or 1% to 60% adds.Composition (f1) definitely measure certainly in many factors, anti-including compositions Answer the form (e.g., gel or rubber) of product and whether with the addition of any other filler.The suitably example of enhancement filler Including chopped strand such as choppedAnd/or enhancement silica filler such as aerosil, silicon dioxide gas Gel, silica xerogel and precipitated silica.Aerosil is to it known in the art, and commercially available obtain ?；As by the Cabot Corporation (Cabot Corporation, Massachusetts, U.S.A.) of Massachusetts, United States with business The pyrogenic silica that name of an article CAB-O-SIL sells.
In terms of the weight of compositions, compositions can the most also with 0.1% to 95% or 1% to 60%,
Or the amount of 1% to 20% comprises composition (f2) increasing filling property filler.The example increasing filling property filler includes rubble English, oxidation Aluminum, magnesium oxide, calcium carbonate (such as winnofil), zinc oxide, Talcum, kieselguhr, ferrum oxide, clay, Muscovitum, titanium dioxide, Zirconium oxide, sandstone, white carbon black, graphite or combinations thereof.Increasing filling property filler is to it known in the art, and commercially available；As By state of West Virginia Berkeley Spring this silicon dioxide company of the U.S. (U.S.Silica, Berkeley Springs, WV) abrasive silica sold with trade name MIN-U-SIL.The winnofil being suitable for includes from Su Wei group (Solvay)SPM and from Sulawesi mining company (SMI)Know 100。
Compositions can the most also comprise composition (f3) conductive filler.Composition (F) can have heat conduction and electric conductivity concurrently.Or Person, composition (F) can be thermally conductive and electrically insulating.Composition (F) is selected from aluminium nitride, aluminium oxide, aluminum trihydrate, Barium metatitanate., oxygen Change beryllium, boron nitride, carbon fiber, diamond, graphite, magnesium hydroxide, magnesium oxide, metal particle, onyx, carborundum, tungsten carbide, Zinc oxide and combinations thereof.Composition (F) can comprise metal packing, inorganic filler, fusible filler or combinations thereof.Metal Filler includes metallic and has the metallic of multilamellar on the surface of described particle.These layers can be (such as) position Metal nitride layer on the surface of described particle or metal oxide layer.The suitably example of metal packing has selected from as follows The particle of metal: aluminum, copper, gold, nickel, silver and combinations thereof, or aluminum.The suitably other example of metal packing is Having the particle of the metal listed above of multilamellar in its surface, described multilamellar is selected from: aluminium nitride, aluminium oxide, copper oxide, oxygen Change nickel, silver oxide and combinations thereof.Such as, metal packing may be included in the aluminum particulate on its surface with alumina layer.
The example of inorganic conductive filler has onyx；Aluminum trihydrate, metal-oxide such as aluminium oxide, beryllium oxide, oxidation Magnesium and zinc oxide；Nitride such as aluminium nitride and boron nitride；Carbide such as carborundum and tungsten carbide；And combinations thereof.Or, The example of inorganic conductive filler has aluminium oxide, zinc oxide and combinations thereof.Fusible filler can include Bi, Ga, In, Sn or Their alloy.Fusible filler also can optionally comprise Ag, Au, Cd, Cu, Pb, Sb, Zn or combinations thereof.The most fusible fill out The example of material includes Ga, In-Bi-Sn alloy, Sn-In-Zn alloy, Sn-In-Ag alloy, Sn-Ag-Bi alloy, Sn-Bi-Cu- Ag alloy, Sn-Ag-Cu-Sb alloy, Sn-Ag-Cu alloy, Sn-Ag alloy, Sn-Ag-Cu-Zn alloy and combinations thereof. Fusible filler can have the fusing point in the range of 50 DEG C to 250 DEG C or 150 DEG C to 225 DEG C.Fusible filler can be that eutectic closes Gold, eutectic alloy or simple metal.Fusible filler is commercially available.
Such as, fusible filler is purchased from Yin Tai scientific & technical corporation of the U.S. (Indium of New York, United States Utica Corporation of America, Utica, N.Y., U.S.A.)；The Arco Buddhist nun of Rhode Island,USA Providence is public Department (Arconium, Providence, R.I., U.S.A.)；And the Hua Jiamei wlding company of Rhode Island,USA Cranston (AIM Solder, Cranston, R.I., U.S.A.).Al filler can be from Japan of such as Illinois, America Naperville U s company (Toyal America, Inc., Naperville, Illinois, U.S.A.) and this torr of California, USA Gram Valimet company (Valimet Inc., Stockton, California, U.S.A.) commercially available.Silver fillers can be from Mei Taile scientific & technical corporation of the U.S. (the Metalor Technologies of State of Massachusetts, US Aunar Er Baile U.S.A.Corp., Attleboro, Massachusetts, U.S.A.) commercially available.
Heat filling is known in the art and commercially available.Such as, CB-A20S and A1-43-Me is can be from Showa What electrician Co., Ltd. (Showa-Denko) was commercially available have varigrained alumina packing, and AA-04, AA-2 and AA18 is can to fill out from Sumitomo Chemical Company Ltd (Sumitomo Chemical Company) commercially available aluminium oxide Material.Zinc oxide, such as, have trade markKnowZinc oxide, can be from U.S. of Pennsylvania, America Mo Naka Guo Xin industry company (Zinc Corporation of America, Monaca, Pennsylvania, U.S.A.) is commercially available.
The shape of filler grain is not particularly limited, but, circular or spheroidal particle can prevent having height in the composition During load filler, viscosity increases to less desirable level.
Composition (F) can be single filler or the combination of different two or more fillers of at least one following character: Such as shape of particle, particle mean size, particle size distribution and wire feeding.For example, it may be possible to advantageously use the combination of filler, such as tool There is the first filler of bigger particle mean size and there is the second filler of less particle mean size.As with not there is this type of filler combination Compositions is compared, and uses to have the first filler of bigger particle mean size and have the second of the particle mean size less than the first filler and fills out Material can improve pack effectiveness and/or can reduce the viscosity of compositions.
The particle mean size of filler will depend upon which many factors, including be selected to composition (F) filler type and add extremely The exact amount of compositions and the final use of composition react product.But, filler can have 0.1 to 80 μm or 0.1 to 50 μm and or 0.1 to 10 μ m in particle mean size.
In compositions, the amount of composition (F) depends on many factors, including being selected to compositions and composition react product Final use, the type of composition (B) and amount and be selected to the type of filler and the amount of composition (F).But, with the body of compositions Long-pending meter, the amount of composition (F) can be at 0 volume % to 80 volume % or 50 volume % to 75 volume % or 30 volume % to 80 bodies In the range of long-pending %.Be not wishing to be bound by theory, it is believed that when filler amount more than 80 volume % time, compositions can react and Form the product that dimensional integrity is insufficient for some is applied.
Compositions can the most also comprise composition (G) inorganic agent.The amount of composition (G) will change depending on such as following factor: The type of selected inorganic agent and the type of pending microgranule (such as composition (F) and/or (D)) and amount, and microgranule is No is to add to processed before in compositions, or microgranule whether treatment in situ.But, with all the components in compositions Weight meter, composition (G) can use with the amount in the range of 0.01% to 20% or 0.1% to 15% or 0.5% to 5%.All As filler, physical dryness agent, the microgranule of some fire retardant and/or some pigment etc can optionally enter with composition (G) when it is present Row surface processes.Microgranule can process with composition (G) before adding compositions, or processes with composition (G) in situ.Composition (G) Alkoxy silane, alkoxy-functional oligosiloxane, cyclic polyorganosiloxane, hydroxyl functional oligomeric's siloxanes such as two can be comprised Methylsiloxane or methyl phenyl siloxane or fatty acid.The example of fatty acid includes stearate, such as calcium stearate.
Some the representative organosilicon filler treatment agents that can serve as composition (G) include that being generally used for processing silicon dioxide fills out The compositions of material, such as organochlorosilane；Organosiloxane；Organic disilazane, such as six alkyl disilazanes；And organic alkoxy Silane, such as C6H13Si(OCH3)3、C8H17Si(OC2H5)3、C10H21Si(OCH3)3、C12H25Si(OCH3)3、C14H29Si(OC2H5)3 And C6H5CH2CH2Si(OCH3)3.Other inorganic agents that can use include alkyl hydrosulfide, fatty acid, titanate esters (titanatc), Titanate coupling agent, zirconium ester coupling agent and combinations thereof.
Or, composition (G) can comprise the alkoxy silane with following formula: R11 mSi(OR12)(4-m), wherein subscript m can have Value in the range of 1 to 3, or subscript m is 3.Each R11Independently be monovalent organic groups, as have 1 to 50 carbon atom, Or 8 to 30 carbon atoms or the univalence hydrocarbyl of 8 to 18 carbon atoms.R11Example have alkyl, such as hexyl, octyl group, dodecane Base, myristyl, cetyl and octadecyl；And aryl, such as benzyl and phenethyl.R11Can be saturated or unsaturated , and be side chain or non-branched.Or, R11It can be saturated and non-branched.
Each R12Independently be the saturated hydrocarbyl with 1 to 4 carbon atom or 1 to 2 carbon atom.It is suitable for use as into The example of the alkoxy silane of point (G) have hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, Dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyl trimethoxy silane, octadecyl trimethoxy Base silane, octadecyltriethoxy silane and combinations thereof.
Alkoxy-functional oligosiloxane is also used as inorganic agent.Such as, suitable alkoxy-functional oligosiloxane Including those of formula (V): (R13O)nSi(OSiR14 2R15)(4-n).In the formula, subscript n is 1,2 or 3, or subscript n is 3.Often Individual R13It can be alkyl.Each R14It can be the unsaturated univalence hydrocarbyl with 1 to 10 carbon atom.Each R15It can be tool There is the unsaturated univalence hydrocarbyl of at least 10 carbon atoms.
Some microgranule (such as metal packing) can process with following material: alkyl hydrosulfide, such as stearylmercaptan；Fatty acid, Such as oleic acid and stearic acid；And combinations thereof.
Inorganic agent for aluminium oxide or passivation aluminium nitride can include the poly-silica of alkoxysilyl functional alkyl methyl Alkane (e.g., R16 oR17 pSi(OR18)(4-o-p) partial hydrolysis condensate or cohydrolysis condensation substance or mixture), or wherein hydrolyzable Group can comprise the similar substance of silazane, acyloxy or oximido.In all these, it is connected to the group of Si, in above formula R16, it is long-chain unsaturation monovalent hydrocarbon or monovalent aromatic official energy hydrocarbon.Each R17Independently be univalence hydrocarbyl, each R18Independently be There is the univalence hydrocarbyl of 1-4 carbon atom.In above formula, subscript o is 1,2 or 3, and subscript p is 0,1 or 2, and precondition is (o+ P) sum is 1,2 or 3.
Other inorganic agents include alkenyl functional polysiloxane.Be suitable for alkenyl functional polysiloxane include (but It is not limited to):
Wherein the value of subscript q is up to 1,500.Other inorganic agents include singly blocking alkoxy-functional polydiorganosiloxanepolyamide Alkane, i.e. one end have the polydiorganosiloxanepolyurea of alkoxyl.The example of this type of inorganic agent is following formula: R25R26 2SiO(R26 2SiO)uSi(OR27)3, wherein the value of subscript u is 0 to 100 or 1 to 50 or 1 to 10 or 3 to 6.Each R25Independently selected from alkyl, Such as Me, Et, Pr, Bu, hexyl and octyl group；And thiazolinyl, such as Vi, pi-allyl, cyclobutenyl and Hex.Each R26It is alkyl independently, Such as Me, Et, Pr, Bu, hexyl and octyl group.Each R27Independently be alkyl, such as Me, Et, Pr and Bu.Or, each R25, each R26And each R27It is Me.Or, each R25It is Vi.Or, each R26And each R27It is Me.
Or, it is possible to the polysiloxane forming hydrogen bond can be used as inorganic agent.Process this strategy profit of filling surface With that assemble or scattered or both forms multiple hydrogen bonds as the means that increase-volume part is tethered to filling surface.Can The polysiloxane average per molecule forming hydrogen bond has at least one silicon binding groups that can form hydrogen bond.This group can It is selected from: there is the organic group of multiple hydroxy functional group or there is the organic group of at least one amido functional group.Can be formed The polysiloxane of hydrogen bond is it is meant that hydrogen bonding is the main connection mode of polysiloxane and filler.Poly-organosilicon Oxygen alkane may not form covalent bond with filler.The polysiloxane that can form hydrogen bond is selected from saccharide-siloxane polymerization Thing, amino-functional polysiloxane and combinations thereof.Or, it is possible to the polysiloxane forming hydrogen bond can be Saccharide-siloxane polymer.
Composition (H) is Biocide.The amount of composition (H) is by depending on including the type of selected Biocide and required useful Effect changes in interior factor.But, in terms of the weight of all the components in compositions, the scope of the amount of composition (H) can be big In 0% to 5%.The example of composition (H) have (h1) antifungal, (h2) herbicide, (h3) insecticide, (h4) antimicrobial or Combinations thereof.
Composition (h1) is antifungal, and such as, these antifungal include the substituted benzimidazole carbamate of N, benzene And imidazolyl carbamate such as 2-benzimidazole ylcarbamic acid methyl ester, 2-benzimidazole aryl urethanes, 2-benzo Imidazole radicals carbamic acid isopropyl ester, N-{2-[1-(N, N-dimethylcarbamoyl) benzimidazolyl] } methyl carbamate, N- { 2-[1-(N, N-dimethylcarbamoyl)-6-tolimidazole base] } methyl carbamate, N-{2-[1-(N, N-dimethyl Carbamyl)-5-tolimidazole base] methyl carbamate, N-{2-[1-(N-methylcarbamoyl) benzimidazolyl] Methyl carbamate, N-{2-[1-(N-methylcarbamoyl)-6-tolimidazole base] } methyl carbamate, N-{2-[1- (N-methylcarbamoyl)-5-tolimidazole base] } methyl carbamate, N-{2-[1-(N, N-dimethylcarbamoyl) Benzimidazolyl] } urethanes, N-{2-[2-(N-methylcarbamoyl) benzimidazolyl] urethanes, N- { 2-[1-(N, N-dimethylcarbamoyl)-6-tolimidazole base] } urethanes, N-{2-[1-(N-methyl ammonia first Acyl group)-6-tolimidazole base] urethanes, N-{2-[1-(N, N-dimethylcarbamoyl) benzimidazolyl] Carbamic acid isopropyl ester, N-{2-[1-(N-methylcarbamoyl) benzimidazolyl] } carbamic acid isopropyl ester, N-{2-[1-(N- Propyl group carbamyl) benzimidazolyl] methyl carbamate, N-{2-[1-(N-butylcarbamoyl) benzimidazolyl] ammonia Base methyl formate, N-{2-[1-(N-propyl group carbamyl) benzimidazolyl] } carbamic acid methoxy acrylate, N-{2-[1-(N- Butylcarbamoyl) benzimidazolyl] carbamic acid methoxy acrylate, N-{2-[1-(N-propyl group carbamyl) benzimidazole Base] } carbamic acid ethyoxyl ethyl ester, N-{2-[1-(N-butylcarbamoyl) benzimidazolyl] carbamic acid ethyoxyl second Ester, N-{1-(N, N-dimethyl carbamyl epoxide) benzimidazolyl] } methyl carbamate, N-{2-[N-methyl carbamyl oxygen Base) benzimidazolyl] methyl carbamate, N-{2-[1-(N-butyl carbamoyloxy group) benzimidazolyl] carbamic acid first Ester, N-{2-[1-(N-propyl group carbamyl) benzimidazolyl] } carbamic acid ethyoxyl ethyl ester, N-{2-[1-(N-butyl ammonia first Acyloxy) benzimidazolyl] carbamic acid ethyoxyl ethyl ester, N-{2-[1-(N, N-dimethylcarbamoyl)-6-chlorobenzene miaow Oxazolyl] } methyl carbamate and N-{2-[1-(N, N-dimethylcarbamoyl)-6-nitrobenzimidazole base] } carbamic acid first Ester；10,10 '-epoxide double fen arsenic (it has trade name vinyzene (Vinyzene), OBPA), two-iodomethyl-p-methylphenyl Sulfone, benzothiophene-2-cyclohexyl Methanamide-S, S-dioxide, (it has phthalimide N-(fluorine dichloromethane sulfenyl) Trade name fluorine folpet (Fluor-Folper) and standby anti-many (Preventol) A3)；Methyl-benzoimidazole-2-aminocarbamic acid Ester (it has trade name carbendazim (Carbendazim) and standby anti-many (Preventol) BCM), double (2-pyridinylthio-1- Oxide) zinc (Zinc Pyrithione), 2-(4-thiazolyl)-benzimidazole, N-phenyl-iodine propargyl-amino formic acid esters, N-octyl group- 4-isothiazoline-3-ketone, 4,5-dichloride-Kathon, N-butyl-1,2-benzisothiazole The combination of the zeolite of quinoline-3-ketone, and/or triazole group compounds, such as Tebuconazole (tebuconazole) and argentiferous.
Composition (h2) is herbicide, and such as, the herbicide being suitable for includes amide herbicide, such as allidochlor (allidochlor) N, N-randox；The chloro-N of CDEA2-, N-diethyl acetamide；Chinese mugwort Buddhist nun third is close (etnipromid) (RS)-2-[5-(2,4-dichlorophenoxy)-2-nitro-phenoxy]-N-ethyl propionamide；Anilide weeding Agent, as cis in cisanilide (cisanilide)-2,5-dimethyl pyrrolidine-1-formailide；Flufenacet (flufenacet) 4 '-fluoro-N-isopropyl-2-[5-(trifluoromethyl)-1,3,4-thiadiazoles-2-base epoxides] acetanilide；Naproanilide (naproanilide) (RS)-α-2-naphthoxy propionanilide；Aryl alanine herbicide, such as suffer (benzoylprop) N-benzoyl-N-(3,4-Dichlorobenzene base)-DL-Alanine；Efficiently wheat straw volt (flamprop-M) N-benzoyl-N-(3- Chloro-4-fluorophenyl)-D-alanine；Chloro-acetanilide herbicide, as chloro-in butachlor (butachlor) N-butoxymethyl-2- 2 ', 6 '-diethyl acetanilide；Metazachlor (metazachlor) 2-chloro-N-(pyrazol-1-yl methyl) acetyl-2 ', 6 '-diformazan Aniline, prynachlor (prynachlor) (RS) the chloro-N-of-2-(1-methyl Propargyl) acetanilide；Sulfonanilide weeding Agent, such as the chloro-2-of cloransulammethyl (Cloransulam) 3-(5-ethyoxyl-7-fluorine [1,2,4] triazol [1,5-c] pyrimidine-2- Base sulfoamido) benzoic acid；Metosulam (metosulam) 2 ', 6 '-two chloro-5,7-dimethoxy-3 '-methyl [1,2,4] three Azoles also [1,5-a] pyrimidine-2-sulfonanilide；Antibiotic herbicide, such as bialaphos (bilanafos) 4-[hydroxyl (methyl) phosphine Acyl]-L-height alanyl-L-Ala-L-Ala；Benzoic acid herbicides, such as Amiben (chloramben) 3-amino-2,5- Dichlorobenzoic acid；2,3,6-TBA2,3,6-trichlorobenzoic acids；Pyrimidine radicals p-methoxybenzoic acid herbicide, such as bispyribac-sodium (bispyribac) double (4, the 6-dimethoxypyridin-2-base epoxide) benzoic acid of 2,6-；Pyrimidine radicals thiobenzoate herbicide, as The chloro-6-of pyrithiobac-sodium (pyrithiobac) 2-(4,6-dimethoxypyridin-2-base sulfur generation) benzoic acid；Phthalic acid weeding Agent, such as chlorthal (chlorthal) tetrachloro-p-phenylene's dioctyl phthalate；Pyridine carboxylic acid herbicide, such as the acid of chlorine Fampridine (aminopyralid) 4-amino-3,6-dichloropyridine-2-formic acid；Quinoline carboxylic acid's herbicide, such as dichloro quinolinic acid (quinclorac) 3,7-dichloroquinoline-8-formic acid.Containing arsenic herbicide, (hydrogen methanearsonic acid) calcium as double in CMA；MAMA hydrogen methyl arsine Acid ammonium, sodium arsenite；Benzoyl cyclohexanedione herbicide, such as mesotrione (mesotrione) 2-(4-mesyl-2- Nitrobenzol formyl) hexamethylene-1,3-diketone；Benzofuranyl alkylsulfonate herbicide, such as benfuresate (benfuresate) 2, 3-dihydro-3,3-dimethyl benzofuran-5-base ethane sulfonate；Carbamate herbicide, such as special azoles prestige (carboxazole) the 5-tert-butyl group-1,2-azoles-3-ylcarbamic acid methyl ester；[(4-is chloro-for 2-for fenoxycarb (fenasulam) 4- Oxy-o-cresyl) acetamido] phenyl sulfonyl amino methyl formate；Phenylamino formic acid esters herbicide, such as BCPC (RS)-sec-butyl 3-chlorobenzene mephenesin Carbamate；Desmedipham (desmedipham) 3-phenylamino formyloxy euphorin, swep (swep) 3,4-Dichlorobenzene base methyl carbamate；Cyclohexene oxime herbicide, as fourth oxygen cyclic ketones (butroxydim) (RS)- (EZ)-5-(3-bytyry-2,4,6-trimethylphenyl)-2-(1-ethoxy imino propyl group)-3-hydroxy cyclohexylphenyl-2-alkene-1- Ketone；Obtain herbicide (tepraloxydim) (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyamino imino group] propyl group }-3-hydroxyl- 5-perhydropyran-4-basic ring hex-2-alkene-1-ketone；Cyclopropyl isoxazole herbicide, such as different chlorine oxadiazon (isoxachlortole) 4-chloro-2-methanesulfonylphenYl 5-cyclopropyl-1,2-azoles-4-base ketone；Dicarboximide herbicide, such as fluphenazine (flumezin) 2-methyl-4-(-three fluoro-tolyls of α, α, α)-1,2,4-diazine-3,5-diketone；Dinitroaniline weeding Agent, such as the fluoro-N-of ethalfluralin (ethalfluralin) N-ethyl-α, α, α-three (2-methacrylic)-2,6-dinitro- Para-totuidine；Aminopropan happy spirit (prodiamine) 5-dipropylamino-α, α, α-three fluoro-4,6-dinitro-ortho-aminotoluene；Two Nitrophenol herbicide, such as the third nitre phenol (dinoprop) 4,6-dinitro-o-cymene-3-alcohol；Etinofen (etinofen) α- Ethyoxyl-4,6-dinitro-ortho-methyl phenol；Diphenyl ether herbicide, such as HC252 (ethoxyfen) O-[2-chloro-5-(2- Chloro-α, α, α-three are fluoro-to toloxyl) benzoyl]-Pfansteihl；Nitrobenzophenone ether herbicide, such as aclonifen (aclonifen) 2-chloro-6-nitro-3-phenoxyaniline；Nitrofen (nitrofen) 2,4 dichloro benzene base 4-nitrobenzophenone ether；Dithiocarbamates Formic acid esters herbicide, such as dazomet (dazomet) 3,5-dimethyl-1,3,5-thiadiazine-2-thioketone；Halogenated aliphatic herbicides, as Dalapon (dalapon) 2,2 dichloropropionic acid；Monoxone；Imidazolidinone weedicide, such as Arsenal (imazapyr) (RS)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-base) nicotinic acid；Inorganic herbicide, such as ten water disodium tetraborates, Azide Sodium；Nitrile herbicide, such as chloroxynil (chloroxynil) 3,5-bis-chloro-4-hydroxy-benzonitrile, ioxynil (ioxynil) 4-hydroxyl Base-3,5-two-iodobenzene formonitrile HCN；Organophosphorus herbicide, as chloro-for phosphoric acid S-4-in anilofos (anilofos) O, O-Methyl disulfide N-cumene glycolamide ester, glufosinate-ammonium (glufosinate) 4-[hydroxyl (methyl) phosphono]-DL-high lactamine；Benzene Epoxide herbicide, such as clomeprop (clomeprop) (RS)-2-(2,4-bis-chloro-toloxyls) propionanilide；Fen Telake (fenteracol) 2-(2,4,5-Trichlorophenoxy) ethanol；Phenoxyacetic acid herbicide, such as MCPA (4-chloro-2-methyl benzene oxygen Base) acetic acid；Phenoxybutyhc acid herbicide, such as MCPB4-(the chloro-oxy-o-cresyl of 4-) butanoic acid；Phenoxypropionic acid herbicide, such as 2, 4,5-tears propanoic acid (fenoprop) (RS)-2-(2,4,5-Trichlorophenoxy) propanoic acid；Aryloxyphenoxypropionic herbicide, as different Grass ether (isoxapyrifop) (RS)-2-[2-[4-(3,5-dichloro-2-pyridyl epoxide) phenoxy group] propiono] isoxazolidine； Phenylenediamine herbicide, such as dinitramine (dinitramine) N1, N1-diethyl-2,6-dinitro-4-trifluoromethyl-m-diaminobenzene.； Pyrazoles epoxide 1-Phenylethanone. herbicide, such as pyrazoxyfen (pyrazoxyfen) 2-[4-(2,4-dichloro-benzoyl base)-1,3-dimethyl Pyrazoles-5-base epoxide] 1-Phenylethanone.；Pyrazolyl phenyl herbicide, such as the chloro-5-of pyraflufen-ethyl (pyraflufen) 2-(4-chloro-5-difluoro Methoxyl group-1-methylpyrazole-3-base)-4-fluorophenoxyacetate；Pyridazine herbicides, such as pyridine, to reach alcohol (pyridafol) 6-chloro- 3-phenyl pyridazine-4-alcohol；Pyridazinone herbicides, such as chloridazon (chloridazon) 5-amino-4-chloro-2-phenyl pyridazine-3 (2H)-one；Grass is rattled away pine (oxapyrazon) 5-bromo-1,6-dihydro-6-oxo-1-phenyl pyridazine-4-base oxamidic acid.；Pyridine weeding Agent, such as fluroxypyr (fluroxypyr) 4-amino-3, the chloro-6-of 5-bis-fluoro-2-pyridyloxy acetic acid；Thiazopyr (thiazopyr) 2-difluoromethyl-5-(4,5-dihydros-1,3-thiazoles-2-base)-4-isobutyl group-6-trifluoromethyl nicotinic acid methyl ester； Thonzylamine herbicide, such as third fixed (iprymidam) 6-chloro-N of grass4-isopropylpyrimidin-2,4-diamidogen；Quaternary ammonium herbicide, Such as the most gloomy fast (diethamquat) 1,1 '-bis-(diethylcarbamoyl methyl)-4,4 '-bipyridyl；N,N'-dimethyl-.gamma..gamma.'-dipyridylium (paraquat) 1,1 '-dimethyl-4,4 '-connection pyrrole；Thiocarbamate herbicide, (cycloate) S-ring as special in Herba Dendrobii Hexyl (ethyl) thioxanthamide；Tiocarbazil (tiocarbazil) S-benzyl di-sec-butyl thiocarbamate； Sulfocarbonate herbicide, as EXD O, O-diethyl-dithio is double (thiocarboxylic)；Thiourea herbicide, such as methiuron (methiuron) tolyl-2-thiourea between 1,1-dimethyl-3-；Triazine herbicides, such as triaziflam (triaziflam) (RS)-N-[2-(3,5-dimethyl phenoxy)-1-Methylethyl]-6-(1-fluoro-1-Methylethyl)-1,3,5-triazines-2,4- Diamidogen；Chlorotriazine herbicide, such as the chloro-N of cyprazine (cyprazine) 6-2-cyclopropyl-N4-isopropyl-1,3,5-triazines-2,4- Diamidogen；The chloro-N of propazine (propazine) 6-2, N4-diisopropyl-1,3,5-triazines-2,4-diamidogen；Methoxyl group triazine weeding Agent, such as prometon (prometon) N2, N4-diisopropyl-6-methoxyl group-1,3,5-triazines-2,4-diamidogen；Methyl mercapto triazine is removed Grass agent, such as cyanatryn (cyanatryn) 2-(4-ethylamino-6-methylsulfany-1,3,5-triazines-2-base amino)-2-methyl-prop Nitrile；Triazinone herbicide, such as hexazinone (hexazinone) 3-cyclohexyl-6-dimethylamino-1-methyl isophthalic acid, 3,5-triazine-2,4 (1H, 3H)-diketone；Triazole-herbicide, such as the third Northey (epronaz) N-ethyl-N-propyl group-3-sulfonyl propyl base-1H-1 that ends, 2, 4-triazole-1-Methanamide；Triazolone herbicide, such as the carfentrazoneethyl chloro-3-{2-of (carfentrazone) (RS)-2-chloro-5-[4- (difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yls]-4-fluorophenyl } propanoic acid；Triazolopyrimidine Pyridine herbicide, such as florasulam (florasulam) 2 ', 6 ', 8-tri-fluoro-5-methoxyl group [1,2,4] triazol [1,5-c] is phonetic Pyridine-2-sulfonanilide；Uracil herbicide, such as fluorine the third platinum chloro-5-of show (flupropacil) 2-(1,2,3,6-tetrahydrochysene-3-first Base-2,6-dioxo-4-trifluoromethyl pyrimidine-1-base) isopropyl benzoate；Carbamide weedicide, such as Alipur-O (cycluron) 3- Ring octyl group-1,1-dimethyl urea；Special azoles grand (monisouron) 1-(the 5-tert-butyl group-1,2-azoles-3-base)-3-MU； Phenylurea herbicide, as grand in chlorine grass (chloroxuron) 3-[4-(4-chlorophenoxy) phenyl]-1,1-dimethyl urea；Tupersan (siduron) 1-(2-methylcyclohexyl)-3-phenylurea；Pyrimidine radicals sulfonylurea herbicide, such as flazasulfuron (flazasulphuron) 1-(4,6-dimethoxypyridin-2-base)-3-(3-trifluoromethyl-2-pyridyl sulfonyl) urea；Pyrrole Sulfometuron Methyl (pyrazosulphuron) 5-[(4,6-dimethoxypyridin-2-base carbamyl) sulfamoyl]-1-methyl pyrrole Azoles-4-formic acid；Triazine radical sulfonylurea herbicide, as thifensulfuronmethyl (thifensulphuron) 3-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-base carbamyl sulfamoyls) thiophene-2-carboxylic acid；Thiadiazolyl group carbamide weedicide, such as terbufos benzthiazuron (tebuthiuron) 1-(the 5-tert-butyl group-1,3,4-thiadiazoles-2-bases)-1,3-dimethyl urea；And/or non-classified herbicide, Such as Fenac (chlorfenac) (2,3,6-trichlorophenyl) acetic acid；Methazole (methazole) 2-(3,4-Dichlorobenzene base)-4- Methyl isophthalic acid, 2,4-bisoxazoline-3,5-diketone；Tritac (tritac) (RS)-1-(2,3,6-trichloro-benzenes methoxyl group) acrylate-2- Alcohol；2,4-D, chlorimuronethyl (chlorimuron) and azoles diclofop-methyl (fenoxaprop)；And combinations thereof.
Composition (h3) is insecticide.The example of the insecticide being suitable for has atrazine (atrazin e), basudin And chlopyrifos (chlorpyrifos) (diazinon).For purposes of this application, insecticide includes insect repellent such as N, N-bis- Ethyl-toluoyl amine；With pyrethroid such as pyrethrin.
Composition (h4) is antimicrobial.The antimicrobial being suitable for is commercially available, such as DOW5700 And DOw5772, it is from the Dow Corning Corporation of Michigan, USA Midland.
Or, composition (H) can comprise containing boron substance, such as boric anhydride, Borax or eight boric acid disodium tetrahydrates；It is permissible Serve as insecticide, antifungal and/or fire retardant.
Composition (I) is stabilizer, its may be used to the reaction rate of compositions compared to containing identical component but save The compositions of this stabilizer changes.Example for the stabilizer of Si-H addition reaction curable compositions has acetylene series alcohols, as Methyl butynol, ethynylcyclohexanol, dimethylated hexynol and 3,5-dimethyl-1-hexin-3-alcohol, ethyl acetylene-3-alcohol, 1-third Alkynes-3-alcohol, 2-methyl-3-butyne-2-alcohol, 3-methyl isophthalic acid-butine-3-alcohol, methylpentynol, 3-phenyl-1-fourth Alkynes-3-alcohol, 4-ethyl-1-octyne-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol and 1-acetenyl-1-Hexalin and they Combination；Cycloalkenyl group type siloxane, such as methylvinylcyclosiloxane class, its example has: 1,3,5,7-tetramethyl-1, and 3,5,7- Tetravinyl cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetra-hexenyl cyclotetrasiloxane and combinations thereof； Alkene-alkine compounds, as 3-methyl-pirylene, 3,5-dimethyl-3-hexene-1-alkynes；Triazole type, such as benzotriazole；Phosphine Class；Thio-alcohol；Hydrazine；Amine, such as tetramethylethylenediamine；Fumaric acid dialkyl, fumaric acid diene ester, anti-butylene two Acid dialkoxy alkyl ester；Maleic acid esters, such as diallyl maleate；Nitrile；Ethers；Carbon monoxide；Olefines, Such as cyclo-octadiene, divinyl tetramethyl disiloxane；Alcohols, such as benzylalcohol；And combinations thereof.
Or, the composition (I) in compositions can be silylated acetylenic compound.It is not wishing to be bound by theory, according to Think and do not contain silylated acetylenic compound or the compositions containing organic alkynol stabilizer (described above those) Si-H addition reaction gained product is compared, and adds silylated acetylenic compound and reduces by compositions hydrosilylation The yellow of the product of preparation.
The example of silylated acetylenic compound have (3-methyl isophthalic acid-butine-3-epoxide) trimethyl silane, ((1,1-bis- Methyl-2-propynyl) epoxide) trimethyl silane, two (3-methyl isophthalic acid-butine-3-epoxide) dimethylsilane, two (3-methyl isophthalic acid- Butine-3-epoxide) silane ethylene methacrylic base silane, two ((1,1-dimethyl-2-propynyl) epoxide) dimethylsilane, methyl (three (1,1-dimethyl-2-propynyl epoxide)) silane, methyl (three (3-methyl isophthalic acid-butine-3-epoxide)) silane, (3-methyl- Ethyl acetylene-3-epoxide) dimethylphenylsilaneand, (3-methyl isophthalic acid-butine-3-epoxide) dimethyhexenes base silane, (3-methyl- Ethyl acetylene-3-epoxide) triethyl silicane, two (3-methyl isophthalic acid-butine-3-epoxide) methyl trifluoro propyl silane, (3,5-diformazans Base-1-hexin-3-epoxide) trimethyl silane, (3-phenyl-ethyl acetylene-3-epoxide) diphenylmethylsilane, (3-phenyl-1-fourth Alkynes-3-epoxide) dimethylphenylsilaneand, (3-phenyl-ethyl acetylene-3-epoxide) dimethylvinylsiloxy base silane, (3-phenyl-1-fourth Alkynes-3-epoxide) dimethyhexenes base silane, (cyclohexyl-1-acetylene-1-epoxide) dimethyhexenes base silane, (cyclohexyl-1- Acetylene-1-epoxide) dimethylvinylsiloxy base silane, (cyclohexyl-1-acetylene-1-epoxide) diphenylmethylsilane, (cyclohexyl-1- Acetylene-1-epoxide) trimethyl silane and combinations thereof.Or, the example of composition (I) have methyl (three (1,1-dimethyl- 2-propynyl epoxide)) silane, ((1,1-dimethyl-2-propynyl) epoxide) trimethyl silane or combinations thereof.Can serve as The silylated acetylenic compound dividing (I) can be prepared by methods known in the art, and described method is such as by by above-mentioned Alkynol and chlorosilane react in the case of there is acid acceptor, make above-mentioned alkynol by silylanizing.
The amount adding the stabilizer to compositions will depend upon which many factors, including required working life, the combination of compositions Thing will be single-component composition or multi-component combination, specifically used stabilizer and composition (C) (if present) Selection and amount.But, in the presence of stabilizer, in terms of the weight of all the components in compositions, the amount of stabilizer can be 0% To 1% or 0% to 5% or 0.001% to 1% or 0.01% to 0.5% and or the model of 0.0025% to 0.025% In enclosing.
Composition (J) is fire retardant.The fire retardant being suitable for can include such as white carbon black, algeldrate and silicate (as Wollastonite), platinum and platinum compounds.Or, fire retardant can be selected from fire retardant based on halogen, such as deca-BDE, eight bromines two Phenylate, HBCD, deca-BDE, two phenoxy group benzene, ethylene be double-tetrabromo phthalimide, pentabromoethyl benzene, Acrylic acid phenyl-pentabromide methyl ester, tribromo phenyl maleimide, tetrabromobisphenol A, double-(tribromophenoxy) ethane, double-(phenyl-pentabromide Epoxide) ethane, poly-dibromobenzene aether, tribromo phenyl allyl ether, double-dibromopropyl ether, tetrabromophthalic anhydride, dibromo new penta Glycol, dibromoethyl dibromo-cyclohexane, penta-BDE, phenylstilbene bromide, pentabromochlorohexane, four xylene bromides, hexabromo ring Dodecane, brominated Polystyrene, ten tetrabromo two phenoxy group benzene, trifluoro propene and PVC.Or, fire retardant can be selected from based on phosphorus Fire retardant, such as (2,3-dibromopropyl)-phosphate ester, phosphorus, cyclic phosphate, triaryl phosphate, the double melamine of pentetic acid (bis-melaminium pentate), tetramethylolmethane bicyclic phosphate, methyl-phosphoric acid dimethyl ester, phosphine oxide glycol, tricresyl phosphate Phenyl ester, tricresyl phosphate-(2-chloroethyl) ester, phosphate ester are (such as tricresyl phosphate, trixylyl phosphate, O, O, O-isodecyl two Phenyl phosphate ester, O, O, O-(ethylhexyl) diphenyl phosphoester), the phosphate (such as ammonium phosphate) of various amine, trioctyl phosphate, Tributyl phosphate or tricresyl phosphate-butoxy ethyl ester.Other fire retardants can include tetraalkyl lead compounds, such as lead tetraethyl, Iron pentacarbonyl, methyl cyclopentadienyl tricarbonyl manganese, tripolycyanamide and derivant (such as melamine salt), guanidine, dicyandiamide, ammonia Base ichthyodin, Alumina hydrate and magnesium hydroxide, Alumina hydrate.
The amount of fire retardant is by depending on all fire retardants as selected and whether there is the factor of solvent etc and change.So And, in terms of the weight of all the components in compositions, in compositions, the amount of fire retardant can be in the range of more than 0% to 10%.
Composition (K) is surface modifier.The suitably example of surface modifier has (k1) adhesion promoter and (k2) releasing agent.Suitable Adhesion promoter for composition (k1) can comprise transition metal chelate, hydrocarbyloxysilane (such as alkoxy silane), alkoxy silane Combination, amino-functional silane or combinations thereof with hydroxyl-functional polysiloxane.Adhesion promoter is to it known in the art, also And can comprise there is formula R19 rR20 sSi(OR21)4-(r+s)Silane, the most each R19Independently be and there are at least 3 carbon atoms Monovalent organic groups；R20Containing at least one, there is the SiC of adhesion promoting groups (such as amino, epoxy radicals, sulfydryl or acrylate-based) Bonding substituent group；Subscript r has the value in the range of 0 to 2；Subscript s is 1 or 2；And (r+s) sum is not more than 3.Or, help viscous Agent can comprise the partial condensate of above silane.Or, adhesion promoter can comprise alkoxy silane and hydroxyl-functional poly organo The combination of alkane.
Or, adhesion promoter can comprise unsaturated compound or epoxide functional compound.Adhesion promoter can comprise unsaturated alkane TMOS or epoxy-functional alkoxy silane.Such as, functionalized alkoxysilane can have formula R22 tSi(OR23)(4-t), Wherein subscript t is 1,2 or 3, or subscript t is 1.Each R22Independently be monovalent organic groups, precondition is at least one R22It is unsaturated organic group or epoxy functionalized organic group.R22The example of epoxy functionalized organic group have 3-(+)-2,3-Epoxy-1-propanol Epoxide propyl group and (epoxycyclohexyl) ethyl.R22The example of unsaturated organic group have 3-methacryloxypropyl, 3- Acryloxypropyl and unsaturated univalence hydrocarbyl (such as vinyl, pi-allyl, hexenyl, undecenyl).Each R23Independent Ground is the saturated hydrocarbyl with 1 to 4 carbon atom or 1 to 2 carbon atom.R23Example have Me, Et, Pr and Bu.
The example of suitable epoxy functionalized alkoxy silane includes that 3-glycidoxypropyltrimewasxysilane, 3-contract Water glycerol epoxide propyl-triethoxysilicane, (epoxycyclohexyl) ethyldimethoxysilane, (epoxycyclohexyl) ethyl diethyl TMOS and combinations thereof.The example of the most unsaturated alkoxy silane includes vinyltrimethoxy silane, alkene Propyl trimethoxy silicane, allyltriethoxysilane, hexenyl trimethoxy silane, undecenyl trimethoxy silicon Alkane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-acryloyl Epoxide propyl trimethoxy silicane, 3-acryloxypropyl triethoxysilane and combinations thereof.
Or, adhesion promoter can comprise epoxy functional silicone, hydroxy-end capped poly organo the most as described above The product of alkane and epoxy functionalized alkoxy silane, or hydroxy-end capped polysiloxane and epoxy functionalized alkoxy silane Physical blending thing.Adhesion promoter can comprise the combination of epoxy-functional alkoxy silane and epoxy functional silicone.Such as, help The example of stick has 3-glycidoxypropyltrimewasxysilane and hydroxy-end capped methyl vinyl silicone to contract with 3- The mixture of the product of water glycerol epoxide propyl trimethoxy silicane or 3-glycidoxypropyltrimewasxysilane Seal with hydroxyl with mixture or the 3-glycidoxypropyltrimewasxysilane of hydroxy-end capped methyl vinyl silicone The mixture of the methyl ethylene/dimethylsiloxane copolymer of end.
Or, adhesion promoter can comprise amino-functional silane, such as amino-functional alkoxy silane, amino-functional alkoxy silane Example have: H2N(CH2)2Si(OCH3)3、H2N(CH2)2Si(OCH2CH3)3、H2N(CH2)3Si(OCH3)3、H2N(CH2)3Si (OCH2CH3)3、CH3NH(CH2)3Si(OCH3)3、CH3NH(CH2)3Si(OCH2CH3)3、CH3NH(CH2)5Si(OCH3)3、CH3NH (CH2)5Si(OCH2CH3)3、H2N(CH2)2NH(CH2)3Si(OCH3)3、H2N(CH2)2NH(CH2)3Si(OCH2CH3)3、CH3NH (CH2)2NH(CH2)3Si(OCH3)3、CH3NH(CH2)2NH(CH2)3Si(OCH2CH3)3、C4H9NH(CH2)2NH(CH2)3Si (OCH3)3、C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3、H2N(CH2)2SiCH3(OCH3)2、H2N(CH2)2SiCH3 (OCH2CH3)2、H2N(CH2)3SiCH3(OCH3)2、H2N(CH2)3SiCH3(OCH2CH3)2、CH3NH(CH2)3SiCH3(OCH3)2、 CH3NH(CH2)3SiCH3(OCH2CH3)2、CH3NH(CH2)5SiCH3(OCH3)2、CH3NH(CH2)5SiCH3(OCH2CH3)2、H2N (CH2)2NH(CH2)3SiCH3(OCH3)2、H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2、CH3NH(CH2)2NH(CH2)3SiCH3 (OCH3)2、CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2、C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2、C4H9NH (CH2)2NH(CH2)3SiCH3(OCH2CH3)2And combinations thereof.
Or, adhesion promoter can comprise transition metal chelate.The transition metal chelate being suitable for includes titanate esters, zirconate (such as acetylacetone,2,4-pentanedione zirconium), aluminium chelate compound (such as aluminium acetylacetonate) and combinations thereof.Or, adhesion promoter can comprise transition metal Chelate and the combination of alkoxy silane, such as glycidoxypropyltrimewasxysilane and aluminium chelate compound or zirconium chelate Combination.
Composition (k2) is releasing agent.The example of the releasing agent being suitable for has fluorinated compound, as fluorine official can organosilicon or fluorine official Can organic compound.
Or, the surface modifier of composition (K) can be used for changing the outward appearance on the product surface of compositions.Such as, table Face modifying agent may be used for increasing the surface gloss of the product of compositions.This surface modifier can comprise and has alkyl Polydiorganosiloxanepolyurea with aryl.Such as, DOW550 fluids be viscosity be 125cSt can be close from the U.S. Have a rest poly-(dimethyl/aminomethyl phenyl) of the commercially available trimethylsiloxy end-blocking of the Dow Corning Corporation of Midland, root state Siloxanes.
Or, composition (K) can be the natural oil obtained by plant or animal origin, such as Semen Lini oil, Oleum Verniciae fordii, Semen sojae atricolor Oil, Oleum Ricini, fish oil, hemp-seed oil, Oleum Gossypii semen, base of a fruit tree oil difficult to understand or Oleum Brassicae campestris.
The definite amount of composition (K) depends on many factors, including the surface modifier being elected to be as composition (K) type and Compositions and the final use of product thereof.But, in terms of the weight of compositions, composition (K) in the presence of, can be with 0.01 weight Amount part adds to compositions to the amount of 50 weight portions or 0.01 weight portion to 10 weight portions or 0.01 weight portion to 5 weight portions In.Composition (K) can be a kind of adhesion promoter.Or, composition (K) can comprise two or more at least one following character side The different surfaces modifying agent that face is different: structure, viscosity, mean molecule quantity, polymer unit and sequence.
Cahin extension agent can include two functional silanes and two functional silicones, and it extends polysiloxane before crosslinking occurs The length of chain.Cahin extension agent can be used for reducing the extension modulus of cured product.Cahin extension agent its react in other compositions of compositions (such as composition (B) and/or composition (C), when it is present) in aliphatic unsaturated group and/or the hydrogen atom competition of silicon bonding.Tool The polydimethylsiloxane having the dimethyl hydrogen siloxy end-blocking of the relatively low degree of polymerization (e.g., 3 to 50 in the range of DP) can be used Make composition (L).Composition (L) can be a kind of cahin extension agent.Or, composition (L) may be embodied in following character at least one The cahin extension agent that different two or more are different: structure, viscosity, mean molecule quantity, polymer unit and sequence.
Composition (M) is end-capping reagent, and described end-capping reagent comprises M unit, i.e. formula R24 3SiO1/2Siloxane unit, the most each R24 Represent unit price nonfunctionalized organic group independently, such as the univalence hydrocarbyl without aliphatic series unsaturated group.Composition (M) can comprise one End is by three Organosilyls such as (CH3)3SiO-blocks, hydrogen atom that the other end is bonded by silicon and/or the unsaturated organic group of aliphatic series The polysiloxane of group's end-blocking.Composition (M) can be polydiorganosiloxanepolyurea, such as polydimethylsiloxane.There is silicon bonding Hydrogen end group and three Organosilyl end groups both polydiorganosiloxanepolyurea can have more than 50% or more than 75% total End group is the hydrogen atom of silicon bonding.In polydimethylsiloxane, the amount of three Organosilyls can be used for regulation by making compositions The modulus of the cured product solidified and prepare.It is not wishing to be bound by theory, it is believed that three Organosilyls of higher concentration End group can provide relatively low modulus in cured product.Composition (M) can be a kind of end-capping reagent.Or, composition (M) can be included in An at least different end-capping reagent of different two or more in following character: structure, viscosity, mean molecule quantity, poly- Compound units and sequence.
Composition (N) is flux.In terms of the weight of all the components in compositions, described compositions can comprise 0% to 2% Flux.Molecule containing chemism functional group (such as carboxylic acid and amine) can be used as flux.This type of flux can include aliphatic series Acid, such as succinic acid, rosin acid, oleic acid and adipic acid；Aromatic acid, such as benzoic acid；Aliphatic amine and derivant thereof, as triethanolamine, The hydrochlorate of amine and the hydrobromate of amine.Flux is to it known in the art, and commercially available.
Composition (O) is age-inhibiting addition.Age-inhibiting addition can comprise antioxidant, UV absorbent, UV stabilizer, Heat stabilizer or combinations thereof.The antioxidant being suitable for is to it known in the art, and commercially available.The antioxidation being suitable for Agent includes the combination of phenol antioxidant and phenol antioxidant and stabilizer.Phenol antioxidant includes complete space sterically hindered phenol With part sterically hindered phenol；And sterically hindered amines, such as tetramethyl piperidine derivant.Suitably phenolic antioxidant include vitamin E and Derive from the U.S.'s different chemical company of vapour Bart (Ciba Specialty Chemicals, U.S.A.) 1010。1010 comprise tetramethylolmethane four (3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester).UV inhales Receive the example of agent include side chain and straight chain 2-(2H-benzotriazole-2-base)-6-dodecyl-4-methyl-phenol (571).The example of UV stabilizer include double (1,2,2,6, the 6-pentamethyl-4-piperidyl) ester of decanedioic acid, 1,2, 2,6,6-pentamethyl-4-piperidyl/decanedioic acid methyl ester and combinations thereof (272).These and otherAdditive is such as765 can be from New York, United States Ta Lidun vapour Bart different chemical company (Ciba Specialty Chemicals, Tarrytown, NY, U.S.A.) commercially available.Other ultraviolet and light stabilizer is commercially available obtains , its example is to derive from the LowLite of Chemtura (Chemtura), derive from the OnCap of Pu Liwan (PolyOne) and derive from U.S. The light of Delaware State E.I.Du Pont Company of state (E.I.du Pont de Nemours and Company, Delaware, U.S.A.) is steady Determine agent 210.Or, it is possible to use oligomeric (higher molecular weight) stabilizer, such as make stabilizer migrate out compositions or its solidification The probability of product minimizes.The example (particularly hindered amine as light stabilizer (HALS)) of oligomeric antioxidative stabilizer is Ciba622, it is and 4-hydroxyl-2, the dimethyl ester of the succinic acid of 2,6,6-tetramethyl-1-piperidine ethanol copolymerization.Heat Stabilizer can include iron oxides and white carbon black, ferrum carboxylate, hydration cerium, barium zirconate, cerium octoate and zirconium caprylate and porphyrin (porphyrin)。
The amount of composition (O) depends on many factors, has including selected specific age-inhibiting addition and required aging resistance Benefit effect.But, in terms of the weight of all the components in compositions, the amount of composition (O) can 0 to 5 weight % or 0.1% to 4% or 0.5 to 3 in the range of weight %.Composition (O) can be a kind of age-inhibiting addition.Or, composition (O) can comprise two Plant or more kinds of different age-inhibiting addition.
Composition (P) is pigment.For purposes of this application, term ' pigment ' includes in order to compositions specifically described herein Product gives any composition of color.The amount of pigment depends on many factors, including selected pigment type and product Expect colourity.Such as, in terms of the weight of all the components in compositions, compositions can comprise 0 to 20% or 0.001% to The pigment of 5%.
The example of pigment being suitable for include indigo, titanium dioxide Stan-Tone50SP01 is green (it can be buied from Pu Liwan) And white carbon black.The representative non-limitative example of white carbon black includes Shawinigan acetylene black, and it can be public from Chevron Phillips Chemical Department (Chevron Phillips Chemical Company LP) buys；Sea by Illinois, USA Fairview highland This pigment company of name (Elementis Pigments Inc., Fairview Heights, IL U.S.A.) is suppliedWhite carbon black (LB-1011)；By Jason Richardson's carbon company of West Germany (Sid in Ohio, USA Akron city Richardson Carbon Co, Akron, OH U.S.A.) SR511 that supplies；With N330, N550, N762, N990 (from U.S. The Degussa engineering carbon company in Pa Xipani city, New Jersey of state (Degussa Engineered Carbons, Parsippany, NJ, U.S.A.)).
Composition (Q) is acid acceptor.Suitably acid acceptor includes magnesium oxide, calcium oxide and combinations thereof.With compositions Weight meter, described compositions can comprise the composition (Q) of 0% to 2%.
In terms of the weight of compositions, compositions can the most also comprise composition (R) rheology of at most 5% or 1% to 2% and add Add agent to improve the rheological characteristic of compositions.Rheologic additive is to it known in the art, and commercially available.Example includes: poly- Amide Polyvest, it can be buied from Ying Chuan company (Evonk)；Disparlon from Jin Shi industrial group；Public from Du Pont The Kevlar Fibre Pulp of department (Du Pont)；From the Rheospan of Nai Nuoke company (Nanocor) with from Lu Borun The Ircogel of company (Lubrizol).Other rheologic additives being suitable for include polyamide wax；Castor oil hydrogenated derivant；With Metallic soap, such as calcium stearate, aluminium stearate and barium stearate, and combinations thereof.
Or, it is the microwax (wax) of solid that composition (R) can be included at 25 DEG C.Fusing point can be selected, so that wax exists The lower value of required application temperature scope has fusing point.It is not wishing to be bound by theory, it is believed that composition (R) serves as improvement combination The processing aid of thing mobility.It is not wishing to be bound by theory, it is believed that the incorporation of wax also can promote that filler mixes, is compounded and takes off Gas (compositions preparation during) and the mixing either statically or dynamically mixing of period (each several part at multi-component combination use). Think that wax serves as processing aid when melted, thus during substantially making mixture filler mix compositions, mixture process itself with And (in use) become easy during de-airing step.The wax with the melt temperature less than 100 DEG C can help to multicomponent group The mixing before application of each several part in compound, even the most such in simple static blender.
The wax being useful as composition (R) can be non-polar hydrocarbon.Wax can have branched structure, ring structure or combinations thereof. Such as, oil microwax be available from the western Babylonish Stone Bi Si company of New York, United States (Strahl ＆ Pitsch, Inc., West Babylon, NY, U.S.A.), and include SP96 (fusing point is in the range of 62 DEG C to 69 DEG C), (fusing point is 73 for SP18 DEG C in the range of 80 DEG C), (fusing point is the scope of 76 DEG C to 83 DEG C for SP19 (fusing point is in the range of 76 DEG C to 83 DEG C), SP26 In), SP60 (fusing point is in the range of 79 DEG C to 85 DEG C), SP617 (fusing point is in the range of 88 DEG C to 93 DEG C), SP89 (fusing point In the range of 90 DEG C to 95 DEG C) and SP624 (fusing point is in the range of 90 DEG C to 95 DEG C).Other oil microwaxes include by U.S. The sub-Compton Co., Ltd in Peter Raleigh, Pennsyivania of state (Crompton Corporation, Petrolia, Pennsylvania, U.S.A.) with trade markThe wax sold.These waxes include 180-W, its comprise saturated side chain and Cyclic non-polar hydrocarbons, and there is the fusing point in the range of 79 DEG C to 87 DEG C；W-445, it comprises saturated side chain And cyclic non-polar hydrocarbons, and there is the fusing point in the range of 76 DEG C to 83 DEG C；WithW-835, it comprises saturated Chain and cyclic non-polar hydrocarbons, and there is the fusing point of 73 DEG C to 80 DEG C.
The amount of composition (R) depends on many factors, and including in selected specific rheologic additive and compositions, other become The selection divided.But, in terms of the weight of all the components in compositions, the amount of composition (R) can be at 0 part to 20 part or 1 part to 15 Part and or 1 part to 5 parts in the range of.Composition (R) can be a kind of rheologic additive.Or, composition (R) can comprise two kinds Or more kinds of different rheologic additive.
Vehicle can be used in the composition.Vehicle can help to the flowing of compositions with some composition (as organic Silicones) introducing.Vehicle used herein contributes to make the composition fluidisation of compositions but does not reacts with composition Those vehicles.Based on dissolubility and the volatility of composition in compositions, vehicle can be selected.Dissolubility is Refer to that vehicle be enough to dissolve and/or the composition of dispersive composition.Volatility refers to the vapour pressure of vehicle.If waving of vehicle The property sent out too high (there is too high vapour pressure), then bubble may be formed during hydrosilylation in the composition, and And these bubbles may cause crack or otherwise weaken or negatively affect the character of product.But, if The volatility of vehicle is not enough (vapour pressure is too low), then vehicle may be with plasticizer shape in the product of compositions Formula remains.
Suitably vehicle includes the polysiloxane with suitable vapour pressure, such as hexamethyl disiloxane, eight first Base trisiloxanes, hexamethyl cyclotrisiloxane and other low-molecular-weight polysiloxane, as available commercially from Michigan, United States The Dow of the 0.5cSt to 1.5cSt of the Dow Corning Corporation of Midland, state200 fluids and DowOS flows Body.
Or, vehicle can comprise organic solvent.Organic solvent can be alcohol, such as methanol, ethanol, isopropanol, butanol Or normal propyl alcohol；Ketone, such as acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK)；Aromatic hydrocarbon, such as benzene, toluene or dimethylbenzene；Aliphatic hydrocarbon, Such as heptane, hexane or octane；Glycol ethers, such as propylene glycol monomethyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol positive third Ether or ethylene glycol n-butyl ether；Halogenated hydrocarbon, such as dichloromethane, 1，1，1-trichloroethane or dichloromethane, chloroform；Dimethyl sulfoxide； Dimethylformamide；Acetonitrile；Oxolane；Chinese liquor；Mineral spirits；Petroleum (naphtha)；Positive methyl pyrrolidone；Or they Combination.
The amount of vehicle will depend upon which many factors, including the type of selected vehicle and be selected to other of compositions The amount of composition and type.But, in terms of the weight of all the components in compositions, the amount of vehicle can 1% to 99% or In the range of 2% to 50%.During preparing described compositions can adding ingredient (S), such as be adapted to assist in mixing and pass Send.After preparing described compositions, can optionally remove all or part of of composition (S).
Composition (T) is surfactant.Suitably surfactant includes organic silicon polyether, ethylene oxide polymer, ring The copolymer of Ethylene Oxide polymer, oxirane and expoxy propane, other nonionic surfactant and combinations thereof. In terms of the weight of all the components in compositions, described compositions can comprise the surfactant of 0% to 0.05%.
Composition (U) is corrosion inhibitor.Suitably the example of corrosion inhibitor include benzotriazole, sulfhydryl benzotriazole with And commercially available corrosion inhibitor, such as the Vanderbilt Co. R. T. from Connecticut, USA Norwalk city The 2 of (R.T.Vanderbilt, Norwalk, Connecticut, U.S.A.), 5-dimercapto-1,3,4-thiadiazole derivant (826) and alkyl thiadiazoles (484).In the presence of composition (U), in terms of the weight of compositions, become The amount dividing (U) can be in the range of 0.05% to 0.5%.
When select above-mentioned composition composition time, overlap can be there is between component type, this is because as herein described certain A little compositions can have more than one function.Such as, some alkoxy silane can be used as filler treatment agent and is used as adhesion promoter, and certain A little plasticizers (such as fatty acid ester) also act as filler treatment agent.Some microgranule can be used as filler and is used as pigment, even serving as Fire retardant, such as white carbon black.When being added to described compositions by supplementary element, described supplementary element is different from each other.
Compositions can be by including all becoming deciliter by any mode easily (the most at ambient temperature or elevated temperature mixing) And prepared by method together.Composition (I) can add, such as when will at high temperature prepare institute when it is present before composition (A) When stating compositions, and/or when described compositions is prepared as single-component composition.
When there is composition (G), compositions can optionally through with composition (G) to particle components (e.g., filler and/or isolation Thing, carries out if present) surface process being mixed with other compositions of described compositions by its product subsequently and prepares.
Or, compositions can be prepared as multi-component combination, such as, when there is not composition (I) or when compositions makes With front will be saved a very long time time.In multi-component combination, composition (A) is stored in has what silicon was bonded with any In composition (such as composition (C)) the separate part of hydrogen atom, and using not long ago being merged by each several part of compositions.Example As, such as can be mixed by any convenient mode, will comprise (B), (A), the composition of (F) and optional above-mentioned one or more Other supplementary elements merge with basis of formation material, prepare two-component composition.Such as can be mixed by any convenient mode, (B), the composition of (C) and optional one or more other supplementary elements above-mentioned will be comprised merge, prepare firming agent.Can be at ring Each composition is merged at border temperature or high temperature.When using two-component composition, the weight ratio of the amount of basestocks and firming agent can be 1 : in the range of 1 to 10: 1.Said composition will be reacted by hydrosilylation, thus form product.This product Can have various ways, such as silane, natural gum, gel, rubber or resin.
Example
These examples are intended to illustrate some embodiments of the present invention, and should not be construed as limiting described in claims The scope of the present invention.Following composition is in example.
Aliphatic series unsaturated compound can be styrene (B1), 1-octene (B2) or 1-hexene (B3), all these also may be used Available from Sigma-Aldrich.Or, aliphatic series unsaturated compound can be the poly dimethyl silicon of (B4) ethenyl blocking Oxygen alkane, silicon bonding ethylene base containing 2.6meq and have 9400 the viscosity of Mw and 200cSt, it can be purchased with DMS-V22 From the lid Le Site company of Pennsylvania, America Mo Lisiweier.SiH functional compound can be (C1) trimethyl first silicon Alkoxy end-capped poly-(methyl hydrogen) siloxanes (" MDHM "), have 1,800 to 2, the SiH of Mw and 2.6meq in the range of 100 Content, it is possible to Le Site company is commercially available with HMS-992 from lid.Or, SiH functional compound can be (C2) phenyl silane (“H3SiPh "), it is available commercially from Sigma-Aldrich.
Comparative catalyst is DOW2-0707INT, it is the complex of Pt and polysiloxane.DOW2-0707INT is available commercially from the Dow Corning Corporation of Michigan, USA Midland.
One or more in following model reaction can be used to test prepared above for as described in composition (A) The catalysis activity of product.Composition (B3) and (C2) is used to comprise PhSiH attempting preparation in [PhSi] reactsz (C6H13)(3-z) product [I].Composition (B3) and (C1) is used to comprise (H attempting preparation in [HMTS] reacts3C)3Si-O-Si(CH2)(C6H13)-O-Si(CH3)3Product [II].
Reference example-formation metal precursor
0.273gm (0.87mmol) is purchased from the anhydrous NiI of Lyme chemical company2Be dissolved in 14.8gmTHF and- Cool down at 35 DEG C.1.64gm (1.84mmol) is purchased from double (trimethyl silyl) Lithamide .s (1 of aldrich companyM THF solution) mixed with 14.8gm THF be incorporated in-35 DEG C at be under agitation slowly added into NiI2In solution.Adding double (front three Base silicyl) after Lithamide. solution, solution becomes dark brown from green/brown.Raise the temperature to room temperature and in stirring Under be heated to 60 DEG C, continue 3 hours.By 0.025MGained solution in the following example be used as precursor.
Example 1-forms metal-ligand complex
Be prepared by the following method precursor solution: by 0.025 mol/L (M) the Ni precursor of concentration mixes with THF, or such as Really this precursor is insoluble in THF, then by this precursor with selected from dimethyl sulfoxide (DMSO), toluene and hexane be used for dissolve part Suitable solvent mixing.Before glycol dimethyl ether nickelous bromide (II) and double trimethyl silyl amino nickel (II) are used as Ni Body.Also by by 0.025MThe part of concentration mixes the solution of every kind of part shown in preparing the most in table 2 with THF.Will With every bottle 85 microlitre, ((μ L) is allocated in 2 milliliters of (mL) bottles every kind of ligand solution prepared above.In order to prepare have to be evaluated The sample as composition (A) of valency, extremely accommodates a kind of interpolation in above-mentioned metal precursor solutions in the bottle of part, and adds The THF of other 85 microlitres (μ L), and under the room temperature of 25 DEG C, vial content is mixed 2 hours with 300RPM.Add enough Metal precursor solutions is so that metal: part ratio is 1: 1 or 1: 2.Gained mixture in bottle is cooled to the temperature of-17 DEG C Degree.Add activator, and allow bottle return to room temperature.Activator is the 0.05 of 95 μ LMThe THF solution of the LiBArF of concentration or NaEt3The toluene solution of BH.Vial content is mixed 2 hours.To the vial content of gained in terms of catalysis Si-H addition reaction Purposes be evaluated.
Example 2-[PhSi] reacts
In order to carry out [PhSi] reaction, by PhSiH3(C2) dodecane solution and 1-hexene (B3) add to according to example In bottle prepared by 1.Add the PhSiH to bottle3(C2) amount is the 6.25 of 170 μ LMThe PhSiH of (in terms of H or SiH)3 (C2) dodecane solution, or 132.4 μ LPhSiH3(C2) solution in 37.6 μ L dodecanes.The amount of 1-hexene (B3) is 145μL.Each bottle is mixed overnight at 50 DEG C (continuing 16 hours).By GC, according to methods described below to each The gained content of bottle is analyzed.
Example 3-[HMTS] reacts
In order to carry out [HMTS] reaction, by 1-hexene (B3) and 1,1,1,3,5,5,5-heptamethyltrisiloxane (C1) adds To according in the bottle prepared by example 1.The amount of the 1-hexene added is 145 μ L.The amount of heptamethyltrisiloxane (C1) is The 3.4 of 312 μ LMThe dodecane solution of the heptamethyltrisiloxane (C1) of concentration (in terms of H or SiH), or 290 μ L seven methyl three silicon The oxygen alkane (C1) solution in 22 μ L dodecanes.Each bottle is mixed overnight at 50 DEG C (continuing 16 hours).By GC, root According to methods described below, the gained content of each bottle is analyzed.
Example 4-GC measures
The sample prepared in the above-described example carries out gas chromatogram (GC) analyze.Use has flame ionisation detector (FID) Hewlett-Packard7890A gas chromatograph carries out GC analysis.Use Leap Combi-Pal robot with from Dynamicization mode is injected.As this system is configured by the detailed description in table 3.
Table 3:GC - FID experiment parameter is arranged.
Carrier gas-99.9998% high-purity helium
Detector-FID, at 280 DEG C, H2=30mL/min, air=300mL/min, tail blows helium=45mL/min
GC entrance, shunts-275 DEG C, split ratio=200: 1, constant voltage (overall flow rate: 22.5 ml/min)
GC post-Agilent low thermal mass post, 350 DEG C, 30m × 320 μ m 0.25 μm
GC temperature program(me)-55 (3) to 300 (5), with 35 DEG C/min, total run time: 15 minutes
Internal standard-containing the dodecane in 5% (w/w) phenyl silane
Data system-Agilent Technologies ChemStation
In the details of GC temperature program(me) such as table 4 below, wherein use the baking oven of 300 DEG C of constant temperature.
Table 4
Use dodecane, as internal standard, chromatography is carried out gravimetric analysis quantitative.Before reactions with 5% (w/w's) The solution of dodecane and phenyl silane introduces internal standard.The theoretical response factor of analyte is calculated and inputs To automatically generate calibration chart and in the presence of internal standard, the concentration of analyte to be carried out quantitative scoring in ChemStation Calculate (equation 1).
RFAnalyte=([analyte]/areaAnalyte) × (areaIs/ [IS]) x RFIs(1)
Term in equation 1 is defined as follows: RFAnalyteThe response factor of=analyte, the concentration of [analyte]=analyte, AreaAnalyteThe peak area of=analyte, areaIs=interior target peak area, [IS]=interior target concentration, RFIs=interior target response because of Son.
In the case of containing experimental error and instrumental error, the relative standard deviation of measurement result is 0.3% to 10% In the range of, this concentration depending on analyte and corresponding yield.Table 5 provides result.
Table 5-result
In table 5, Ni-1 is glycol dimethyl ether nickelous bromide, and Ni-2 is double trimethyl silyls amino nickel (II).

Claims (9)

1. a method, described method includes:
(1) composition that will comprise Ni precursor and part merges, thus prepares product, wherein meets following condition (II):
Described Ni precursor has formula (i) Ni-A2, the most each A independently be the monovalent organic radicals containing at least one silicon atom Group, and
Described part is formula (xviii), wherein
Formula (xviii) isWherein A132、A133And A134Be each independently selected from alkyl or Hydrogen, and A131And A135It is each independently selected from aryl or halogenated aryl.
Method the most according to claim 1, wherein:
Described part is the 10453 of following formula
3., according to the method described in claim 1 or claim 2, described method also includes that (2) by described product and are gone back Former dose of merging.
4. a method, described method includes:
(1) composition that will comprise Ni precursor and part merges, thus prepares product, wherein meets following condition (I):
Described Ni precursor has formula (i) Ni-A2, the most each A independently be the monovalent organic radicals containing at least one halogen atom Group, and
Described part is formula (xviii), wherein
Formula (xviii) isWherein A132、A133And A134Be each independently selected from alkyl or Hydrogen, and A131And A135It is each independently selected from aryl or halogenated aryl.
Method the most according to claim 4, wherein:
Described part is the 10453 of following formula
6. according to the method described in claim 4 or claim 5, described method also include (2) by described product with from Sub-activator merges.
7. a compositions, described compositions comprises:
(A) by the product prepared according to the method according to any one of claim 13；With
(B) aliphatic series unsaturated compound, described aliphatic series unsaturated compound average per molecule has and one or more can carry out The unsaturated organic group of aliphatic series of hydrosilylation；And
(c) poly-organohydrogensiloxanes.
8. a compositions, described compositions comprises:
(A) by the product prepared according to the method according to any one of claim 46；
(B) aliphatic series unsaturated compound, described aliphatic series unsaturated compound average per molecule has and one or more can carry out The unsaturated organic group of aliphatic series of hydrosilylation；With
(C) formula R4 eSiHfSilane, wherein subscript e is 0,1,2 or 3；Subscript f is 1,2,3 or 4, and precondition is (e+f) sum It is 4, and each R4Independently be halogen atom or monovalent organic groups.
9., according to the compositions described in claim 7 or claim 8, wherein said compositions also comprises one or more additionally Composition, one or more other compositions described are different from composition (A), (B) and (C), and are selected from: (D) spacer；(E) Extender, plasticizer or combinations thereof；(F) filler；(G) filler treatment agent；(H) Biocide；(I) stabilizer；(J) fire-retardant Agent；(K) surface modifier；(L) cahin extension agent；(M) end-capping reagent；(N) flux；(O) age-inhibiting addition；(P) pigment；(Q) acid Receptor；(R) rheologic additive；(S) vehicle；(T) surfactant；(U) corrosion inhibitor；And combinations thereof.
CN201280045402.2A 2011-09-20 2012-09-20 Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst Active CN103814040B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161536799P 2011-09-20 2011-09-20
US61/536,799 2011-09-20
PCT/US2012/056202 WO2013043785A2 (en) 2011-09-20 2012-09-20 Nickel containing hydrosilylation catalysts and compositions containing the catalysts

Publications (2)

Publication Number Publication Date
CN103814040A CN103814040A (en) 2014-05-21
CN103814040B true CN103814040B (en) 2016-08-31

Family

ID=55456473

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280045402.2A Active CN103814040B (en) 2011-09-20 2012-09-20 Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst

Country Status (5)

Country Link
US (1) US9545624B2 (en)
EP (1) EP2758416B8 (en)
JP (1) JP6101695B2 (en)
CN (1) CN103814040B (en)
WO (1) WO2013043785A2 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2996804B1 (en) * 2013-05-15 2020-12-30 Momentive Performance Materials Inc. Activation of metal salts with silylhydrides and their use in hydrosilylation reactions
WO2014201082A1 (en) 2013-06-12 2014-12-18 Arizona Board Of Regents On Behalf Of Arizona State University First-row transition metal hydrogenation and hydrosilylation catalysts
JP6333710B2 (en) * 2014-06-12 2018-05-30 国立研究開発法人産業技術総合研究所 Method for producing organosilicon compound and catalyst composition
US10000515B2 (en) 2014-08-12 2018-06-19 Kyushu University, National University Corporation Hydrosilylation reaction catalyst
JP6327426B2 (en) 2014-08-12 2018-05-23 国立大学法人九州大学 Hydrosilylation catalyst
JP6761997B2 (en) 2014-08-19 2020-09-30 国立大学法人九州大学 Hydrosilylated iron catalyst
US10058542B1 (en) 2014-09-12 2018-08-28 Thioredoxin Systems Ab Composition comprising selenazol or thiazolone derivatives and silver and method of treatment therewith
WO2016099727A2 (en) * 2014-12-19 2016-06-23 Dow Corning Corporation Ligand components, associated reaction products, activated reaction products, hydrosilylation catalysts and hydrosilylation curable compositions including the ligand components, and associated methods for preparing same
KR102564637B1 (en) 2015-07-14 2023-08-08 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation reaction catalyst
CN106881131B (en) * 2015-12-15 2019-11-12 中国科学院大连化学物理研究所 A kind of supported non-precious metal catalyst and its preparation and the application in nitrile synthesis
WO2017126562A1 (en) 2016-01-22 2017-07-27 信越化学工業株式会社 Novel isocyanide compound and hydrosilylation reaction catalyst
EP3590596B1 (en) 2017-02-28 2023-07-12 Kyushu University, National University Corporation Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction
CN113244963B (en) * 2021-05-17 2022-05-27 杭州师范大学 Polyethylene glycol N, P coordination non-noble metal catalyst, preparation thereof and application thereof in olefin catalytic hydrosilylation reaction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787045A (en) * 2010-02-08 2010-07-28 浙江大学 Method for catalyzing hydrosilylation with ruthenium compound
CN102179266A (en) * 2011-03-18 2011-09-14 杭州师范大学 Supported catalyst for hydrosilylation and preparation method thereof

Family Cites Families (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3296291A (en) 1962-07-02 1967-01-03 Gen Electric Reaction of silanes with unsaturated olefinic compounds
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
NL131800C (en) 1965-05-17
NL129346C (en) 1966-06-23
US3516946A (en) 1967-09-29 1970-06-23 Gen Electric Platinum catalyst composition for hydrosilation reactions
JPS4925649B1 (en) * 1970-03-13 1974-07-02
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3989667A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US3989668A (en) 1975-07-14 1976-11-02 Dow Corning Corporation Method of making a silicone elastomer and the elastomer prepared thereby
US4087585A (en) 1977-05-23 1978-05-02 Dow Corning Corporation Self-adhering silicone compositions and preparations thereof
US4284751A (en) 1980-05-14 1981-08-18 Products Research & Chemical Corp. Polyurethane sealant system
US4370358A (en) 1980-09-22 1983-01-25 General Electric Company Ultraviolet curable silicone adhesives
US4550152A (en) 1983-10-28 1985-10-29 General Electric Company Nickel complex catalyst for hydrosilation reactions
US4584355A (en) 1984-10-29 1986-04-22 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-I
US4591622A (en) 1984-10-29 1986-05-27 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product thereof
US4585836A (en) 1984-10-29 1986-04-29 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-II
JPS61195129A (en) 1985-02-22 1986-08-29 Toray Silicone Co Ltd Production of organosilicon polymer
JP2512468B2 (en) 1987-04-13 1996-07-03 鐘淵化学工業株式会社 Curable resin composition
US4766176A (en) 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
US4784879A (en) 1987-07-20 1988-11-15 Dow Corning Corporation Method for preparing a microencapsulated compound of a platinum group metal
JP2630993B2 (en) 1988-06-23 1997-07-16 東レ・ダウコーニング・シリコーン株式会社 Granules containing platinum-based catalyst for hydrosilylation reaction and method for producing the same
JPH0214244A (en) 1988-06-30 1990-01-18 Toray Dow Corning Silicone Co Ltd Thermosetting organopolysiloxane composition
EP0434840B1 (en) 1989-02-28 1995-02-22 Kanegafuchi Chemical Industry Co., Ltd. Organic polymer, preparation thereof, and curable composition comprising same
US5036117A (en) 1989-11-03 1991-07-30 Dow Corning Corporation Heat-curable silicone compositions having improved bath life
US5063267A (en) 1990-11-28 1991-11-05 Dow Corning Corporation Hydrogen silsesquioxane resin fractions and their use as coating materials
JP3029680B2 (en) 1991-01-29 2000-04-04 東レ・ダウコーニング・シリコーン株式会社 Organopentasiloxane and method for producing the same
GB9103191D0 (en) 1991-02-14 1991-04-03 Dow Corning Platinum complexes and use thereof
JP2511348B2 (en) 1991-10-17 1996-06-26 東レ・ダウコーニング・シリコーン株式会社 Organopolysiloxane and method for producing the same
CA2139356C (en) 1992-07-01 2001-02-06 Donna J. Crowther Transition metal olefin polymerization catalysts
US5248715A (en) 1992-07-30 1993-09-28 Dow Corning Corporation Self-adhering silicone rubber with low compression set
TR199700681T1 (en) * 1995-01-24 1998-02-21 E.I. Du Pont De Nemours And Company alpha-olefins and olefin polymers and related processes.
US5683527A (en) 1996-12-30 1997-11-04 Dow Corning Corporation Foamable organosiloxane compositions curable to silicone foams having improved adhesion
US6034240A (en) 1998-03-09 2000-03-07 Symyx Technologies, Inc. Substituted aminomethylphosphines, coordination complexes of aminomethylphosphines and their synthesis
US6350916B1 (en) 1998-04-17 2002-02-26 Symyx Technologies, Inc. Selective oxidation of alcohols to aldehydes or ketones
JP3444199B2 (en) 1998-06-17 2003-09-08 信越化学工業株式会社 Thermal conductive silicone rubber composition and method for producing the same
US6974878B2 (en) 2001-03-21 2005-12-13 Symyx Technologies, Inc. Catalyst ligands, catalytic metal complexes and processes using same
US6521793B1 (en) 1998-10-08 2003-02-18 Symyx Technologies, Inc. Catalyst ligands, catalytic metal complexes and processes using same
US20020010291A1 (en) 1998-12-04 2002-01-24 Vince Murphy Ionic liquids and processes for production of high molecular weight polyisoolefins
AU2165000A (en) 1998-12-04 2000-06-19 Symyx Technologies, Inc. Combinatorial discovery and testing of ionic liquids
JP2000169513A (en) * 1998-12-09 2000-06-20 Mitsui Chemicals Inc Olefin polymerization catalyst and process
US6177519B1 (en) 1999-03-02 2001-01-23 Exxon Chemical Patents, Inc. Silane grafted copolymers of an isomonoolefin and a vinyl aromatic monomer
US6197714B1 (en) * 1999-03-23 2001-03-06 Cryovac, Inc. Supported catalysts and olefin polymerization processes utilizing same
US6362309B1 (en) 1999-04-01 2002-03-26 Symyx Technologies, Inc. Polymerization catalyst ligands, catalytic metal complexes and compositions and processes using and method of making same
WO2001019786A1 (en) 1999-09-10 2001-03-22 Symyx Technologies Catalyst ligands, catalytic metal complexes and processes using and methods of making same
US6177585B1 (en) 2000-05-19 2001-01-23 Dow Corning Corporation Bimetallic platinum catalysts for hydrosilations
US7078164B1 (en) 2000-06-19 2006-07-18 Symyx Technologies, Inc. High throughput screen for identifying polymerization catalysts from potential catalysts
US6790298B2 (en) 2000-07-10 2004-09-14 Tini Alloy Company Method of fabrication of free standing shape memory alloy thin film
CN1184243C (en) * 2000-09-14 2005-01-12 中国科学院化学研究所 Process for preparing long-chain branched polyethylene elastomer
WO2003010207A1 (en) 2001-07-23 2003-02-06 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalyst for polymerization or copolymerization of olefins, preparation and use of the same
RU2004132221A (en) * 2002-04-04 2005-09-10 Дегусса АГ (DE) BISPHOSPHINS AS BIDENTATE LIGANDS
ATE363504T1 (en) 2002-05-01 2007-06-15 Dow Corning ORGANOHYDROGENSILICON COMPOUNDS
CN100354372C (en) 2002-05-01 2007-12-12 陶氏康宁公司 Compositions having improved bath life
DE10257938A1 (en) 2002-12-12 2004-06-24 Oxeno Olefinchemie Gmbh Production of complexes of Group 6-10 elements, useful for hydroformylation, hydrogenation, coupling and polymerization reactions, involves reaction of Group 6-10 metal with unsaturated nitrogen containing compounds
GB0305927D0 (en) 2003-03-14 2003-04-23 Ic Innovations Ltd Compound
GB0306430D0 (en) 2003-03-20 2003-04-23 Bp Chem Int Ltd Polymerisation and oligomerisation catalysts
US7538228B2 (en) * 2003-12-17 2009-05-26 The Penn State Research Foundation Oxazoline ligands for asymmetric catalysis
RU2394039C2 (en) * 2004-02-26 2010-07-10 Телен С.А.С. Metal complexes for use in atom or group transfer and olefin exchange reactions
CN1976965B (en) 2004-03-17 2012-10-10 陶氏环球技术有限责任公司 Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
CN1260233C (en) * 2004-04-02 2006-06-21 中国科学院上海有机化学研究所 Chirality phosphine ligand, synthesis, and application in asymmetric catalyfic reaction
JP2005306994A (en) 2004-04-21 2005-11-04 Shin Etsu Chem Co Ltd Silicone emulsion composition for forming coating film
GB0410749D0 (en) 2004-05-14 2004-06-16 Dow Corning Ireland Ltd Coating apparatus
CN100537018C (en) 2004-06-16 2009-09-09 陶氏环球技术公司 Apparatus and method for Ziegler-Natta research
CN1315573C (en) * 2005-01-07 2007-05-16 吉林大学 Beta-diimide nickel compound/alkyl aluminium catalyst system and its application
US20090286678A1 (en) 2005-05-02 2009-11-19 Symyx Technologies, Inc. High Surface Area Metal And Metal Oxide Materials and Methods of Making the Same
KR101519805B1 (en) 2005-09-15 2015-05-12 다우 글로벌 테크놀로지스 엘엘씨 Catalytic olefin block copolymers with controlled block sequence distribution
CN101326255B (en) 2005-12-08 2013-09-25 陶氏康宁公司 Continuous process for production of silicone pressure sensitive adhesives
CN100344656C (en) * 2006-05-11 2007-10-24 复旦大学 Process for preparation of polynorbornene
CN100395268C (en) * 2006-05-11 2008-06-18 复旦大学 N-N double teeth ligand, three-coordination monovalence nickel olefin polymerization catalyst, and its prepn. method
US8101251B2 (en) 2006-07-03 2012-01-24 Dow Corning Corporation Chemically curing all-in-one warm edge spacer and seal
KR20090074039A (en) 2006-10-10 2009-07-03 다우 코닝 코포레이션 Extenders for organosiloxane compositions
EP1925623A1 (en) 2006-11-24 2008-05-28 Total Petrochemicals Research Feluy Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes.
JP5349806B2 (en) * 2007-01-30 2013-11-20 三洋化成工業株式会社 Urethane resin composition
GB0708347D0 (en) 2007-05-01 2007-06-06 Dow Corning Polymer compositions
GB0724914D0 (en) 2007-12-21 2008-01-30 Dow Corning Moisture curable compositions
US9103019B2 (en) * 2008-02-01 2015-08-11 American Air Liquide, Inc. Metal precursors containing beta-diketiminato ligands
BRPI1005404A2 (en) * 2009-02-06 2016-07-05 Dow Global Technologies Inc isomerization / hydroalumination catalyst and process for preparing a trialkyl aluminum compound
WO2010104534A1 (en) 2009-03-12 2010-09-16 Dow Corning Corporation Thermal interface materials and mehtods for their preparation and use
EP2411474A1 (en) 2009-03-23 2012-02-01 Dow Corning Corporation Chemically curing all-in-one warm edge spacer and seal
US8236915B2 (en) * 2009-07-10 2012-08-07 Momentive Performance Materials Inc. Hydrosilylation catalysts
CN101613425B (en) * 2009-07-21 2011-05-04 浙江大学 Catalyst of polyethylene with double peak and/or broad peak molecular weight distribution
WO2012071360A1 (en) 2010-11-24 2012-05-31 Momentive Performance Materials Inc. Metal - catalyzed mono - hydrosilylation of polyunsaturated compounds
WO2012071358A2 (en) * 2010-11-24 2012-05-31 Momentive Performance Materials Inc. In-situ activation of metal complexes containing terdentate nitrogen ligands used as hydrosilylation catalysts
CN104245132B (en) 2012-04-17 2017-09-22 莫门蒂夫性能材料股份有限公司 High activated catalyst and its preparation method for hydrosilylation reactions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787045A (en) * 2010-02-08 2010-07-28 浙江大学 Method for catalyzing hydrosilylation with ruthenium compound
CN102179266A (en) * 2011-03-18 2011-09-14 杭州师范大学 Supported catalyst for hydrosilylation and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Base Adducts of β-Ketoenolates. III. Complexes of Cobalt(II) and Nickel(II);Joyce T. Hashagen, John P. Fackler et al.;《Jonrnal of the American Chemical Society》;19650705;第87卷(第13期);2821-2824 *
Metal Chelates of N-benzothiazol-2-yl-,N-benzoxazol-2-yl- and N-(1H-benzimidazol-2-yl)-benzamide;Jorge Angulo-Cornejo,Maria Lino-Pacheco et al.;《Inorganica Chimica Acta》;20000714;第305卷(第1期);38-45 *
Studies of Nitro Complexes. I. Some Nitrito Cmoplexes of Nickel(II);D.M.L.Goodgame et al.;《Inorganic Chemistry》;19641001;第3卷(第10期);1389-1394 *

Also Published As

Publication number Publication date
JP2014528940A (en) 2014-10-30
WO2013043785A3 (en) 2013-06-27
EP2758416A2 (en) 2014-07-30
JP6101695B2 (en) 2017-03-22
CN103814040A (en) 2014-05-21
EP2758416B8 (en) 2018-08-01
US20140183398A1 (en) 2014-07-03
US9545624B2 (en) 2017-01-17
EP2758416B1 (en) 2018-05-09
WO2013043785A2 (en) 2013-03-28

Similar Documents

Publication Publication Date Title
CN103814040B (en) Nickeliferous hydrosilylation catalyst and the compositions containing this catalyst
CN103842368B (en) Iridium containing hydrosilylation catalysts and compositions containing the catalysts
CN103958059B (en) Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use
CN103946228A (en) Cobalt containing hydrosilylation catalysts and compositions containing the catalysts
CN104024264A (en) Ruthenium containing hydrosilylation catalysts and compositions containing catalysts
CN104024267A (en) Iron containing hydrosilylation catalysts and compositions containing the catalysts
CN103814038A (en) Ruthenium containing hydrosilylation catalysts and compositions containing catalysts
CN103814037A (en) Manganese containing hydrosilylation catalysts and compositions containing the catalysts
CN107207546A (en) Ligand component, correlated response product, reaction product, the hydrosilylation catalysts comprising the ligand component and the hydrosilylation curable compositions of activation, and for preparing their correlation technique
KR20140041578A (en) Hydrosilylation reaction curable compositions and methods for their preparation and use
US20140182483A1 (en) Titanium Containing Hydrosilylation Catalysts And Compositions Containing The Catalysts
CN103857685A (en) Vanadium containing hydrosilylation catalysts and compositions containing the catalysts
US20140187783A1 (en) Hafnium Containing Hydrosilylation Catalysts and Compositions Containing the Catalysts
US20140225027A1 (en) Silver Containing Hydrosilylation Catalysts And Compositions Containing The Catalysts
US20140228573A1 (en) Zirconium Containing Hydrosilylation Catalysts and Compositions Containing the Catalysts
US20140231703A1 (en) Molybdenum Containing Hydrosilylation Reaction Catalysts and Compositions Containing the Catalysts
US20140206863A1 (en) Copper Containing Hydrosilylation Catalysts and Compositions Containing the Catalysts

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: michigan

Patentee after: Dow organosilicon company

Address before: michigan

Patentee before: Dow Corning

CP01 Change in the name or title of a patent holder